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Standard Practice forOXIDATION-REDUCTION POTENTIAL OF WATER1

This standard is issued under the fixed designation O 1498: the number immediately following the designation indicates theyear of original adoption or. in the case of revision, the year of last revision. A number in parentheses indicates the year of lastfeapproval. A superscript cpsilon («) indicates an editonal change since the last revision or reipprovii.

" NOTE—New Section 7,9 was editorially added in December I982.

1. Scope1.1 This practice covers the apr:i;atus and

procedure for the electrometric measurementof oxidation-reduction potential (ORP) in wa-ter. It does not deal with the manner in whichthe solutions are prepared, the theoretical in-terpretation of the oxidation-reduction poten-tial, or the establishment of a standard oxida-tion-reduction potential for any given system.The practice described has been designed forthe routine and process measurement of oxi-dation-reduction potential.

2. Applicable Documents2.1 A STM Standards:D 1129 Definitions of Terms Relating to Wa-

ter2

D 1193 Specification for Reagent Water2

D 3370 Practices for Sampling Water2

3. Summary of Practice3.1 This is a practice designed to measure the.

ORP which is defined as the electromotiveforce between a noble metal electrode and areference electrode when immersed in a solu-tion. The practice describes the electronicequipment available to make the measurementand describes how to determine the sensitivityof the electrodes as well as the calibration ofequipment to solutions having a known poten-tial. The ORP electrodes are inert and measurethe ratio of the activities of the. oxidized to thereduced species in the process reactions.

4. Definitions4.1 The term "oxidation- • :ction poten-

tial" used in this method is defined in accord-ance with Definitions D 1 1 29 as follows:

4. 1 . 1 oxidation-reduction potential — the elec-tromotive force developed by a noble metalelectrode immersed in the water, referred to thestandard hydrogen electrode.

4.1.2 The oxidation-reduction potential(ORP) of a process solution can be describedas the millivolt signal Em, produced when anoble metal electrode and a reference electrodeare placed in water. The millivolt signal pro-duced can be represented as follows:

2.3 log Xo,/

where:'!.•>*E°

FRT

-ORP,»constant that depends on the

choice of reference electrodes.- Faraday constant,- gas constant,»absolute temperature, °C -t-

273.15,/t - number of electrons involved

in process reaction, andAot and Ar*i » activities of the reactants in the

process.

4.2 For definitions of other items used inthis method, refer to Definitions D 1129.

1 This practice is under the jurisdiction of ASTM CommitteeD-19 on Water and is the direct responsibility of SubcommitteeD 19.09 on Saline and Brackish Water.

Current edition approved Sept. 24. 1976. Published Novem-ber 1976. Originally published as O 1498 - 57 T. Last previousedition D 1498- 59(1970).

J Annual Book of ASTM Standards. Vol 11.01.

263

5. iBterfereaces5.1 The ORP electrodes reliably measured

ORP in nearly all aqueous solutions and ingeneral are not subject to solution interferencefrom color, turbidity, colloidal matter, and sus-pended matter.

5.2 The ORP of an aqueous solution is sen-sitive to change in temperature of the solution,but temperature correction is rarely done dueto its minimal effect and complex reactions.Temperature corrections are usually appliedonly when it is desired to relate the ORP to theactivity of an ion in the solutions.

5.3 The ORP of an aqueous solution is sen-sitive to pH variations when the oxidation-re-duction reaction involves either hydrogen orhydroxyl ions. The ORP generally tends toincrease with an increase in hydrogen ions andto decrease with an increase in hydroxyl ionsduring such reactions.

5.4 Reproducible oxidation-reduction po-tentials cannot be obtained for chemical sys-tems that are not reversible. The measurementof end point potential in oxidation-reductiontitration is sometimes of this type.

5.5 If the metallic portion of the ORP elec-trode is sponge-like, materials absorbed fromsolutions may not be washed away, even byrepeated rinsings. In such cases, the electrodemay exhibit a memory effect, particularly if itis desired to detect a relatively low concentra-tion of a particular species immediately after ameasurement has been made in a relativelyconcentrated solution. A brightly polishedmetal electrode surface is required for accuratemeasurements.

5.6 The ORP resulting from interactionsamong several chemical systems present inmixed solutions may not be assignable to anysingle chemical.6. Apparatus

6.1 Meter—Most laboratory pH meters canbe used for measurements of ORP by substi-tution of an appropriate set of electrodes andmeter scale. The characteristics of a variety oflaboratory meters are shown in Table 1. Thechoice will depend on the accuracy desired inthe determination.

6.1.1 Most process pH meters can be usedfor measurement of ORP by substitution of anappropriate set of electrodes and meter scale.

D1498

These instruments are generally much morerugged than those which are used for veryaccurate measurements in the laboratory. Usu-ally, these more rugged instruments produceresults that are somewhat less accurate andprecise than those obtained from laboratoryinstruments. The characteristics of three typesof process ORP analyzers are presented in Ta-ble 2. Each of these analyzers is satisfactory forprocess ORP measurements. The choice of ana-lyzer is generally .based on how closely thecharacteristics of the analyzer match the re-quirements of the application. Typical factorswhich may be considered include, for example,the types of signals which the analyzer canproduce to drive external devices, and the spanranges available.

6.1.2 For remote ORP measurements the po-tential generated can be transmitted to an ex-ternal indicating meter. Special shielded cableis required to transmit the signal.

6.2 Reference Electrode—A calomel, silver-silver chloride, or other reference electrode ofconstant potential shall be used. If a saturatedcalomel electrode is used, some potassium chlo-ride crystals shall be contained in the saturatedpotassium chloride solution. If the referenceelectrode is of the flowing junction type, thedesign of the electrode shall allow for eachmeasurement a fresh liquid junction to beformed between the solution of potassium chlo-ride and the standard or the test solution. Theelectrode design shall also allow traces of so-lution to be washed from the outer surfaces ofthe electrodes. To ensure the desired slow out-ward flow of the reference-electrode solution,the solution pressure inside the liquid junctionshould be somewhat in excess of that outsidethe junction. In nonpressurized applicationsthis requirement can be met by maintaining theinside solution level higher than the outsidesolution level. If the reference electrode is ofthe nonflowing junction type, these outwardflow and pressurization considerations shall notapply. The reference electrode and junctionshall perform satisfactorily as required in theprocedure for checking sensitivity described inSection 9.

6.3 Oxidation-Reduction Electrode—A noblemetal is used in the construction of oxidation-reduction electrodes. The most common metalsemployed are: platinum, gold, and silver. It is

important to select aby the test solution,electrode shall be simetal comes in com.The area of the nobletest solution should b

6.4 Electrode As:electrode holder or ;for laboratory measistyles of electrode heious process appUcatiin an open tank, pivessel, or a high pres

7. Reagents and Ma7.1 Purity of R

chemicals shall beotherwise indicated,agents shall conformCommittee on An;American Chemicamay be used, provithat the reagent is ofpermit its use withouthe determination.

7.2 Purity of Wancatcd, reference to wmean reagent waterlions D 1193, Type

7.3 Aqua Regia—trated nitric acid (r-volumes of concert(HC1, spgr 1.18). Itenough solution berequirements.

7.4 Buffer Standabuffer salts availableof Standards specificstandard buffer solunumbers and drying

7.4.1 Phthalate I-(pH. - 4.00 at 25potassium hydrogenwater and dilute to

7.4.2 Pho(pH. - 6.86tassium dihy<ggen3.53 g of anhphate (Na2HP€>; in

7.5 Chromic-Acii.solve about f\(KjCr2O7) in 535 m

264

f t R 3 0 0 8 0 2

h mored for veryitory. Usu-ts producecurate andlaboratory

three typesated in Ta-sfactory forJiceofana-closely thetch the re-ical factors}r example,laiyzer canad the span

cnis the po-d to an en-sided cable

met, silver-:lectrode ofa saturatedissium chlo-le saturatede reference•n type, thew for each

i to beissium chlo->luiion. Theraces of so-surfaces of

:d slow out-de solution,.lid junctionthat outsideapplicationsntaining thethe outsidectrode is of:se outwardons shall notnd junctionuired in thedescribed in

it—A noblef oxidation-unon metalsi silver. It is

important to select a metal that is not attackedby the test solution. The construction of theelectrode shall be such that only the noblemetal comes in contact with the test solution.The area of the noble metal in contact with thetest solution should be approximately 1 cm2.

6.4 Electrode Assembly—A conventionalelectrode holder or support can be employedfor laboratory measurements. Many differentstyles of electrode holders are suitable for var-ious process applications such as measurementsin an open tank, process pipe line, pressurevessel, or a high pressure sample line.

7. Reagents and Materials7.1 Purity of Reagents—Reagent grade

chemicals shall be used in all tests. Unlessotherwise indicated, it is intended that all re-agents shall conform to the specifications of theCommittee on Analytical Reagents of theAmerican Chemical Society.3 Other gradesmay be used, provided it is first ascertainedthat the reagent is of sufficiently high purity topermit its use without lessening the accuracy ofthe determination.

7.2 Purity of Water—Unless otherwise indi-cated, reference to water shall be understood tomean reagent water conforming to Specifica-tions D 1193, Type II.

7.3 Aqua Regia—Mix 1 volume of concen-trated nitric acid (HNO3, sp gr 1.42) with 3volumes of concentrated hydrochloric acid(HCl sp gr 1.18). It is recommended that onlyenough solution be prepared for immediaterequirements.

7.4 Buffer Standard Salts—Table 3 lists thebuffer salts available from the National Bureauof Standards specifically for the preparation ofstandard buffer solutions. The NBS includednumbers and drying procedures.

7.4.1 Phthalate Reference Buffer Solution(pH. - 4.00 at 25°C)— Dissolve 10.12 g ofpotassium hydrogen phthalate (KHdHtOO inwater and dilute to 1 L.

7.4.2 Phosphate Reference Buffer Solution(pH. - 6.86 at 25°C)—Dissolve 3.39 g of po-tassium dihydrogen phosphate (KH2PO4) and3.S3 g of anhydrous disodium hydrogen phos-phate (NajHPO4) in water and dilute to 1 L.

7.5 Chromic Acid Cleaning Solution—Dis-solve about 5 g of potassium dichromate

in 500 mL of concentrated sulfunc

D1498

acid (H2SO4, sp gr 1.84).7.6 Detergent—Use any commercially

available "low-suds" liquid or solid detergent.7.7 Citric Acid (I + I)—Mix equal volumes

of concentrated nitric acid (HNO3, sp gr 1.42)and water.

7.8 Redox Standard Solution; Ferrous-FerricReference Solution4—Dissolve 39.21 g of fer-rous ammonium sulfate (Fe(NR»)3-(SO4)2 •6H2O), 48.22 g of ferric ammonium sulfate(FeNR,(SO4)j. l2H2O)and 56.2 mL of sulfuricacid (HjSO4, sp gr 1.84) in water and dilute to1 L. It is necessary to prepare the solution usingreagent grade chemicals that have an assayconfining them to be within 1 % of the nominalcomposition. The solution should be stored ina closed glass or plastic container.

7.8.1 The ferrous-ferric reference solution isa reasonably stable solution with a measurableoxidation - reduction potential. Table 4 pre-sents the potential of the platinum electrode forvarious reference electrodes at 25 °C in thestandard ferrous-ferric solution.. 7.9 Redox Reference Quinhydrone Solu-

tions—Mix 1 L of pH 4 buffer solution, see7.4.1, with 10 g of quinhydrone. Mix 1 L of pH7 buffer solution, see 7.4.2, with 10 g of quin-hydrone. Be sure that excess quinhydrone isused in each solution so that solid crystals arealways present. These reference solutions arestable for only 8 h. Table 5 lists the nominalmillivolt redox readings for the quinhydronereference solutions at temperatures of 20°C,25°C, and 30°C.

8. Sampling8.1 Collect the samples in accordance with

Practices D 3370.

9. Preparation9.1 Electrode Treatment—Condition and

maintain ORP electrodes as recommended bythe manufacturer. If the assembly is in inter-mittent use, the immersible ends of the elec-

1 "Reagent Chemical*. American Chemical Society Spec-ifications," Am. Chetn. Sot, Washington, D. C. For suciet-tioos on die testing of reagents not listed by the AmericanChemical Society, see "Reagent Chemicals and Standards,"by Joseph Rosin, D. Van Nottrand Co.. Inc, New York.N. Y., and "The United States Pharmacopeia.''

' "Standard Solution for Redox Potential Measurements,"Analytical Chemistry. Vol 44. 1972, p. 1038.

265

D 1498

trodc should be kept in water between mea-surements. Cover the junctions and fill-holes ofreference electrodes to reduce evaporation dur-ing prolonged storage.

9.2 ORP Electrode Cleaning—Removetraces of foreign matter. Immerse the oxidation-reduction electrode in warm aqua regia (70°C)and allow to stand for a period of about 1 min.This solution dissolves the noble metal as wellas any foreign matter so that the electrodeshould not be allowed to stand in it longer thanthe time specified. The above treatment in aquaregia may also be used cautiously to recondi-tion an electrode that has become unreliable inits operation. It is also possible to clean theelectrode in HNO3 (1 + 1). Warm the solutionand electrode gradually to boiling. Maintain itjust below the boiling point for about 5 minand then allow the solution and electrode tocool. Wash the electrode in water several times.It is desirable to clean the electrode daily. Analternative cleaning procedure is to immersethe electrode at room temperature in chromicacid cleaning mixture and then rinse first withdilute hydrochloric acid and then thoroughlywith water. Preliminary cleaning with a deter-gent sometimes is desirable to remove oily res-idues. A mild abrasive can be used to removesome paniculate matter. In these cleaning op-erations particular care must be exercised toprotect the glass-metal seals from suddenchanges of temperature, which might crackthem.

10. Calibration and Standardization10.1 Before using electronic type meters,

turn them on and allow them to warm upthoroughly. Bring them to electrical balance bycarefully following the manufacturer's instruc-tions. Set the scale or range to the desiredmillivolt level expected in the test solution.

10.2 Verify the sensitivity of the electrodesby noting the change in millivolt reading whenthe pH of the test solution is altered. The ORPwill increase when the pH of the test solutiondecreases and the ORP will decrease if the testsolution pH is increased. Place the sample in aclean glass beaker and agitate the sample. Insertthe electrodes and note the ORP or millivoltreading. Add a small amount of a dilute NaOHsolution and note the value of the ORP. If theORP drops sharply when the caustic is added.

the electrodes are sensitive and operatingproperly. If the ORP increases sharply whenthe caustic is added, the polarity is reversedand must be corrected in accordance with themanufacturer's instructions. If the ORP doesnot respond as above when the caustic is added,the electrodes should be cleaned as describedin 9.2 and the above procedure repeated.

10.3 Checking Response Electrodes to theStandard Redox Solutions (see 7.8 and 7.9)—Wash the metal and reference electrode andthe sample cup or container with three changesof water or by means of a flowing stream froma wash bottle. Fill the sample container withfresh redox standard solution and immerse theelectrodes. Turn the range switch to the properrange and engage the operating button. Adjustthe asymmetry control to the millivolt potentialof the standard redox solution. Without chang-ing the setting of the asymmetry potential knob,repeat the above procedure until two successiveinstrument readings are constant. The readingsshould not differ from the millivolt value of thestandard redox solution by more than 10 mV.

10.3.1 It usually suffices to check the sensi-tivity of the electrodes since the important fea-ture is the change of potential as related to theconcentration of the oxidant or reductant pres-ent. The actual numerical value of the potentialwill vary depending on the constituents presentin the water.

10.4 Indirect Calibration and Standardiza-tion:

10.4.1 Employ this procedure when it is notconvenient or practical to remove the electrodesfrom the flowing stream or container in whichthe ORP is being determined. Use of a labo-ratory ORP meter or an additional analyzer isrequired.

10.4.2 Verify the sensitivity of the laboratoryORP meter or additional process analyzer inaccordance with 10.2.

10.4.3 Collect a grab sample that is repre-sentative of the material that is in contact withthe electrodes of the analyzer that is to bestandardized. If a submersion-style electrodechamber is in use, collect the sample from thedischarge of the chamber. Immediately trans-port the sample to the laboratory ORP meteror additional process analyzer and measure theORP. It is absolutely essential that the samplebe representative of the solution in contact with

the electrodes oand that the inttained until itsparticular, the teremain constantlion control on tibrated until thORP of the samscribed above urobtained that di ~This procedure cof the solutionmore than 10 rrlion.

10.4.4 The sealso be verifiedcentration of thgrab sample c.10.4.3. It is necetions required inthis method ofFor example, thtion can be usedORP electrode sline chlorination

11. Procedure11.1 After the

for sensitivity (scribed in 10.4, vchanges of watestream from a w;a clean glass beathe electrodes,throughout the rrmillivolt potentiaficient time for thsuccessive portioion two successi%than 10 mV. Astabilize probablORP.

11.2 Continualof Flowing StreaiORP analyzers welectrode chamb-surements whichmatic control. Mand electrode ch;

266

operating,rply whens reversed,e with theORP doesc is added,described

ated.ies to theind 7.9)—trode and:e changesream fromainer withimerse thethe properDR. Adjustt potential>ut chang-itial knob,successivee readingsilueofthen 10 mV.the sensi-mant fea-'-d to the

t pres-potentialts present

ndardiza-

n it is not:lectrodesin which

>f a labo-nalyzer is

iboratoryalyzer in

is repre-tact withis to be:lectrodefrom thely trans-,P meterisure the: sample'.act with

the electrodes of the analyzer being adjustedand that the integrity of the sample be main-tained until its ORP has been measured. Inparticular, the temperature of the sample mustremain constant. Then adjust the standardiza-tion control on the process analyzer being cal-ibrated until the reading corresponds to theORP of the sample. Repeat the procedure de-scribed above until two successive readings areobtained that differ bv no nore than 10 mV.This procedure cannotoe employed if the ORPof the solution being tested is fluctuating bymore than 10 mV at the time of standardiza-tion.

10.4.4 The sensitivity of the electrodes canalso be verified by a determination of the con-centration of the oxidants or reductants In agrab sample collected in accordance with10.4.3. It is necessary, to determine the condi-tions required in each individual system to usethis method of verifying electrode sensitivity.For example, the chlorine residual determina-tion can be used to verify the sensitivity of anORP electrode system used to control an alka-line chlorination-cyanide destruction system.

11. Procedure11.1 After the assembly has been checked

for sensitivity (10.2) or standardized as de-scribed in 10.4, wash the electrodes with threechanges of water or by means of a flowingstream from a wash bottle. Place the sample ina clean glass beaker or sample cup and insertthe electrodes. Provide adequate agitationthroughout the measurement period. Read themillivolt potential of the solution allowing suf-ficient time for the system to stabilize. Measuresuccessive portions of the sample until readingson two successive portions differ by no morethan 10 mV. A system that is very slow tostabilize probably will not yield a meaningfulORP.

11.2 Continuous Determination of the ORP• of Flowing Streams or Batch Systems—ProcessORP analyzers with their ragged electrodes andelectrode chambers provide continuous mea-surements which are the basis for fully auto-matic control. Make selection of the electrodesand electrode chamber to suit the physical and

01498

chemical characteristics of the process material.Locate the submersion-style electrode chamberso that fresh solution representative of the proc-ess stream or batch continuously passes acrossthe electrodes. Agitation may be employed inorder to make the stream or batch more nearlyhomogeneous. The ORP value is usually dis-played continuously and can be noted at anyspecific time. Frequently, the pH value is con-tinuously recorded, yielding a permanent rec-ord.

12. Calculation12.1 If the meter is calibrated in millivolts,

read the oxidation-reduction potential directlyfrom the meter scale. This ORP potential isrelated to the reference electrode used in themeasurement.

12.2 Calculate the oxidation-reduction po-tential of the sample, in millivolts, referred tothe hydrogen scale as follows:

E* - £„*. + E^fwh'ere:£* » oxidation-reduction potential referred

to the hydrogen scale, mV,Eob, " observed oxidation-reduction potential

of the noble metal-reference electrodeemployed, mV, and

Enf — oxidation-reduction potential of the ref-erence electrode as related to the hydro-gen electrode, mV.

13. Report13.1 Report the oxidation-reduction poten-

tial to the nearest 10 mV, interpolating themeter scale as required. When considered ap-propriate, the temperature at which the mea-surement was made, the electrode system em-ployed, and the pH at the time of measurement,may also be reported.

14. Precision and Accuracy14.1 Precision and accuracy of the measure-

ment depends largely on the condition of theelectrode system and on the degree to whichthe chemical system being measured fits thequalifications given in Sections 3 and 5. In theabsence of substances that coat or poison theelectrode, the precision is ± 10 mV.

267

A R 3 0 0 8 0 5

4SIl> D 1498

T.M. 1 Ufcor,,orv ORP M.tert——— —— —— — .Range: ~~ —— —————

NormalExpanded

Scale*NormalExpanded

AccuracyRepeatabilityAsymmetry potential compensator- —————— ———— __ —

1 — —————— —— _Type 1

0 - ±1400 mV

10

= 7•.iyes

— • ————— - ——— .

Type 11—— ———— - ——— .

0 - ±1400 mVany 200 mV

101= 1=0.5yes

——— —— - ———— .

Type in

0 - ±1400 mV»ny 140 mV

101±0.7±0.2yes

• ——— ——— - ———

Type IV—— - ——— - ————

0 - ±1400 mV

0.1

±0.1±0.2yes

— —————— ——

T.b,, 2 ORP

Range

StabilityOutput signal, full scale:

Potentiomemc

Current

Type I200, 500, or 1000 mV with

lower limit between±700 mV

±2 mV/24 h

10,100 mV1.5V4 to 20. 10 to 50mA

Type II0 to 1000 mV

±0.06 mV/week

1. 1.0 V

Oto 16,0 to 20. 4 to 20. 5to 25. 10 to SO mA

Type HI

100 to 200 mV

±0.1% of span

4 to 20. 10 to 50mA

T«Me 3 Nation! Bire.ii of StMdirds (NBS) Mttttitlt tor Reference Buffer SoJ.tfols

NBS Standard SampleDesignation* Buffer Salt Drying Procedure

186-H-C186-I-C185-e

disodium hydrogen phosphatepotassium dihydrogen phosphatepotassium hydrogen phthalate

2 h in over at 130° C2 h in over at 130* Cdrying not necessary

' The buffer salts listed can be purchased from the Office of Standard Reference Materials. National Bureau ofStandards, Washington. D.C. 20234.

Tibfc 4 PoleitU of tkc Ptetfen Electro* forSeven! Refemce Electrodes it 25'C to Fciron-Ferric

Reference Electrode

Hg. H«, a,, said KG 'Ag, AgCl. 1 .00 M KCIAg. AgO. 4.00 M KCIAg. AgCl. said KCIPt. H, (p - 1). H(a = I)

Potential EMF.mV

+ 430+ 439+ 475+ 476+ 675

' —— — — —— —— . ———— ———— — ——— . ______

Buffer solution, nominal pHTemperature. *CReference Electrode

Silver/silver chlorideCalomel

____ Hyd roge n~ ———— ——— - —————

———— • —— ——• ———— —— ——

20

268223470

———— - ——— —

——— i —————— — —— .

425

3632\8462

———————

ORP~——— — • ———

30

258213454

• —— • — —— —

——— ' —————- mV. ——————— _

20

9247

295——— —————

—— - ———————— ——

725

8641

285™ — —in—.

—— •• ——

——— • ——— - ——— __

30

7934

275 .———— ——

X 1.1 Meaning of the Tmeasurement establishes tf-reductants prevailing wi th iwaste water. The meayurcontrast, for example, toThe ORP electrode pair •-.potential of a solution. B>ability to oxidize or reducemay be determined.

X I . 2 Use ofORPComrXI.2.1 ORP measurem

trial process control to miunwanted materials whichtion or reduction. Frequensolution is to be treated, ution-reduction profile of ttdieted with some accuracycategory are found in thecyanide is oxidized to cyanato carbon dioxide and nitrelent-chromium is reducedORP Measurements are usin both instances if the pitrolled.

XI .2 .2 In addition to cwhich a specific material iiments can be used to contnif a correlation can be estabing ORP and the reaction irpie is the use of ORP measu

'of municipal waste b\ chlorthe extent of odor productiiAlso, sewage treatment pifrom unwanted oxidizing ormight harm treatment mateinfluent is monitored.

X1.3 Temperature Effrcments:

XI.3 .1 The effect ofMeasurements can be undithe Nernst equation;

£ = £' - 2.3R:nl

where£ = measured potential£° = potential when all ci

The American Society for Teiconnection with any item mennontof any such patent rights, and tnr

This standard is subject to reviand if not revised, either reappro\<standards and should be addressee.responsible technical committee. Hmake vour views kno*n to the AS

268

D 1498

l>pe IV

:UOO rnV APPENDIX

(Nonmandatory Information)

XI. OXIDATION REDUCTION POTENTIAL

111mV

span

10 50 mA

.•ciry

I Bureau of

30

-934

\I 1 Meaning of the Term ORP -The ORP,Tiea>urement establishes the ratio of oxidams and

prevai l ing w i t h i n a solution of wa te r orwate r . The measurement is nonspecific in

contrast. for example, to the pH measurement.The ORP electrode pair senses the prevai l ing net

of a so lu t ion . B> this measurement, theto oxidize or reduce species in the solution

'^av be determined,X l , 2 Use of ORP Control of Waste Processes:XI 2,1 ORP measurements are used in indus-

t r i a l process control to monitor the t reatment ofunwanted materials w h i c h are amenable to oxida-tion or reduction. Frequent ly , only one species in,olutton is to be treated, in which case the oxida-tion-reduction profile of the process can be pre-dicted wi th some accuracy. Two examples in thiscategory are found in the plat ing industry: Wastecyanide is oxidized to cyanate and then (if required)io carbon dioxide and ni trogen, and waste hexava-lem-chrormum is reduced to the tnvalent state.ORP Measurements are useful for process controlin both instances if the pH is constant and con-trolled.

X I . 2 . 2 tn addition to control of processes inwhich a specific material is treated. ORP measure-ments can be used to control nonspecific processesif a correlation can be established between prevail-ing ORP and the reaction in the process. An exam-ple is the use of ORP measurements in odor controlof municipal waste by chlormation. In some cases,the extent of odor production correlates with ORP.Also, sewage treatment plants may be protectedfrom unwanted oxidizing or reducing agents whichmight harm treatment materials if the ORP ot theinfluent is monitored.

X I , 3 Temperature Effects on ORP Measure-ments:

X 1.3,1 The effect of temperature on ORPMeasurements can be understood by consideringthe Nernst equation:

RTE » £' - 2.3 4: log Q

nrwhere£ = measured potential£° = potential when all components involved in

the reaction are at unit activity and 253 C,R = gas constant.T = absolute temperature, t' C +• 273.15.F = Faraday,n = number of electrons involved in the reaction.

andQ = product of the activities of the oxidants di-

vided by the product of the activities of thereductants. each activity raised to that powerwhose exponent is the coefficient of the sub-stance in the applicable chemical reaction.

Changes in £° with temperature produce the samechanges in £. Further , the slope of the curve thatrelates £ and 7" depends directly on T Final ly ,changes in act ivi ty with temperature will producechanges in £.

XI.3.2 Automatic temperature compensation isseldom attempted in ORP Measurements, due tothe appearance of n in the prelogarithmic factor ofthe Nernst equation. The slope" of the plot of £versus T thus depends not only on T. but on n aswell, so that different amounts of compensation are

.required, depending on the value of n. If the proc-ess under study is well characterized and the valueof n known, automatic temperature compensation ispossible. However, if the value of n is unknown orvariable (see XI.2.1). then compensation is notpossible.

XI.4 Polarity Check-The polarity of the inputof the analyzer may also be determined by connect-ing a battery of known polarity and observing thedeflection of the meter. A resistive voltage dividermay be connected between the battery and ana-lyzer, if necessary, to prevent the meter from beingdriven off-scale due to application of an excessivelyhigh potential.

X I , 5 Increase Precision of Measurement. If aprecision of greater than 5 mV is desired, controlthe temperature of the assembly to within s 1° C.Higher precision will require closer control of tem-perature. Electrodes, test solutions, and wash watermust be allowed to stand for a sufficient time toobtain thermal equilibrium at the temperature ofmeasurement, in order to reduce to a negligiblevalue the effects of the thermal or electrical hyster-esis of the reference electrode.

The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted inconnection wan any item mentioned in this standard. Users of this standard are expressly advised that determination of the validityof any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five yearsand if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additionalstandards and should be addressed to ASTM Headauarters. Your comments-will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake vour views known to the ASTM Committee on Standards. 1916 Race St.. Philadelphia. Pa. 19103.

269

A R 3 Q 0 8 0 7

AW* * 10

U.S. ENVIRONMENTAL PROTECTION AGENCY SAS NUMBERCLP SAMPLE MANAGEMENT OFFICEP.O. BOX 818 - ALEXANDRIA, VIRGINIA 22313PHONE: 703/557-2490 - FTS/557-2490

SPECIAL ANALYTICAL SERVICESClient Request

Regional Transmittal Telephone Request

A. EPA Region/Client;EPA-REGION III-ARCS III

B. RSCC Representative; COLLEEN WALLING

C. Telephone Number; (301) 266-9180

D. Date of Request:____________

E. Site Name; AIW FRANK. CHESTER COUNTY, PA

Please provide below description of your request for SpecialAnalytical Services under the Contract Laboratory Program. Inorder to most efficiently obtain laboratory capability for yourrequest, please address the following considerations, ifapplicable. Incomplete information may result in a delay in theprocessing of your request. Please continue response on additionalsheets, or attach supplementary information as needed.

1. General Descrition of analytical services requested:

Extraction of 6 soil samples by the TCLP Extraction methodwith the extracts being analyzed for the organic TCLPParameters by the 3/90 CLP Organic SOW and SW-846, Method8150. Add pyridine and 3 methylphenol to the semivolatilemethod target list. See Attachment 2 for the full TCLPconstituent list.

2. Definition and number of work units involved (specify whetherwhole samples or fractions; whether organics or inorganics;whether aqueous or soil and sediments; and whether low,medium, or high concentration):

6 low/medium concentration soil samples and 2 rinsate blanksto be subjected to the TCLP extraction procedure and theextracts analyzed for the organic TCLP parameters. AnalyzeVOAs, BNAs, and Pesticides by the 3/90 CLP SOW and theherbicides by SW 846, Method 8150.

3. Purpose of analysis (specify whether Superfund (enforcement orremedial action), RCRA, NPDES, etc.):

RI/FS - ARCS III

SAS Approved By (signature):Date:

. H R 3 0 0 8 0 8

4. Estimated date(s) of collection:

To be determined.

5. Estimated date(s) and method of shipment:

To be determined.

Samples will be shipped overnight by overnight air carrier.This schedule is tentative and is dependant on the projectremaining on schedule. Sampling may continue into the week of

6. Number of days analysis and data required after laboratoryreceipt of samples:

Completed data packages are due within 35 days from receipt oflast sample.

7. Analytical protocol required (attach copy if other thanprotocol currently used in this program):

TCLP Extraction - Appendix II of 40 CFR 261.

TCLP Organic Parameters Analysis (VOAs, BNAs, Pesticides)by the 3/90 CLP Organic SOW.

TCLP Herbicide Analysis by SW 846, Method 8150.

Results are to be reported in ug/L.

8. Special technical instructions (if outside protocolrequirements, specify compound names, GAS numbers, detectionlimits, etc.):

9. Analytical results required (if known, specify format for datasheets, QA/QC reports, Chain-of-Custody documentation, etc.).If not completed, format of results will be left to programdiscretion:

All raw data. Deliverables as per the CLP SOWs. In addition,copies of TCLP extraction log book, signed and dated copy ofchain-of-custody documentation, copies of air bill confirmingsample receipt, and SAS Request Form are also required. TCLPextraction must be indicated on all Form I's.

10. Other (use additional sheets or attach supplementaryinformation, as needed):

Laboratory must comply with the CSF requirements asspecified in the 3/90 SOW. Laboratory will beresponsible for the disposal of all sample remnants andextracts.

11. Name of sampling/handling contact:

Jeff Orient - NUS Corporation(412)-788-1080.

A.R300809

12. Data Requirements:Precision Desired

Parameter________Detection Limit_____(+/-% or Concentration)

TCLP organic compounds As per 3/90 CLP SOW As per 3/90 CLP SOWand SW 846, and SW 846,Method 8150 Method 8150

13. QC Requirements:Limits

Audits Required___Frequency of Audits (Percent or Concentration)


See Attachment 1 for additional requirements.

14. Action Required if Limits are Exceeded:

As per 3/90 CLP SOW.

15. Request Prepared By:

Gregory L. Zimmerman - NUS Corporation - (412) 788-1080June 6, 1991; revised September 5, 1991.

16. Request Reviewed By (CRL use only):Date:

Please return this request to the Sample Management Office as soonas possible to expedite processing of your request for SpecialAnalytical Services. Should you have any questions or need anyassistance, please contact your local Regional representative atthe Sample Management Office.

AR3008IQ

ATTACHMENT 1

13. QC Requirements: For TCLP Organics by OLM01.0 (3/90), followQC requirements specified in the SOW with the following deviations.

13. A. All TCLP target compounds must be spiked. Report allrecoveries but do not perform recovery correction. Chlordane andToxaphene will require separate leachate aliquots for the matrixspike because of their multicomponent responses. Generation ofsufficient leachate volume for spiking may require the lab to spikeleachate aliquots from more than one sample. Matrix spikeduplicates are not required except for herbicides if volume allowsas stated below.

13. B. Pyridine and 3-Methylphenol must be added to thesemivolatile analysis. Achieve the following criteria for Pyridineand 3-Methylphenol:* Calibrate at 5 levels.* Minimum relative response factor o.OlO* Quantitate using the internal standard with the closest retentiontime (must be free of interferences) to the Pyridine and 3-Methylphenol peaks individually.* Quantitate using the most abundant m/z that is free ofinterferences. Major ions for Pyridine are 79, 52, 51 and 50(descending abundance). Major ions for 3-Methylphenol are 107, 108,77, 79, 90. If coelution occurs among some, or all of theMethylphenol isomers, the quantitation method and the final report(Form Is) must reflect the sum of the isomers (e.g., Total 2 and3-Methylphenol or Total Cresol).

13.C. For analysis of 2,4-D, 2,4,5-T, 2,4,6-T and Silvex, followQC specified in SW 846 method 8150.* Perform a matrix spike (60-120% recovery) and, if volume allows,a matrix spike duplicate (<30 RPD).* Perform a sample duplicate (<30 RPD).* Perform a method blank (<MDL for all target compounds).* If greater than %50 separation cannot be achieved for 2,4,5-T and2,4,6-T, quantitate and report as total Trichlorophenol.

flR3008! I

^11804 Federal Register / Vol. 55. No. 61 / Thursday. March 29. 1990 / Rules and Regulations

-slculated regulatory level (i.e.. thechronic toxicity reference level

iltiplied by the DAF) is below thelytical quantitation limit, the

quantitation limit!» the final regulatorylevel. Note that the lift of constituent* inTable fl.2 contains the 14 constituent!currently regulated under the existing

EPTC As specified in today's rule, theseconstituents will continue to beregulated at their current levels.

TABLE n.2.--Toxicrn' CHARACTERISTIC CONSTITUENTS AND REGULATORY LEVELS

EPA HWNO '

D004DOOSO018O006O019O0?0D021D022O007D023D024

— D025D0260016DC27D028DC29D030 •DO '.2D031X22X33X34XOBX13X»9»14»35 1X336

•C39015 • 'O40 •0*1 . - -

~b42-017

043

ConcCluvnl (mg/L)

A-ten.c _j i .I i— i

torutne ——————————————————————————————— — •

CNorobenztfW ————————————————————————————————

rr-Trw)' 1. jnrt*« [«*-••'mj-^m^ 3^««.T(a^, lfi« »___•<r-C'tff . ,fi.jr«k<&»i 4^M - ----- ,.- ,. , . „Cf»«M , _..- , , - - ,,. - - --- • - - - -

1 4.D*chiorobf._?«n_. ,. _. .... _ ... .. . , , „ _ . ,._,1,?.p hlOrn»m»n _ , , - - _ , , _ _ Tr- ,,.._,,, _,, _1 1 •DicWoro.Mhy.cf.f.

End'in .... ..___«.,.....,,_. .... ,,, ,

Ha»r*lnmfe*n»n*HexaCW0.9-1.3-buta!ji*Oe ———— . ——————————————————————————————

Iw* , .

u^nfty ,.,, _MemorycrUo. __._._.....„ , _ .„,.,., ._...,,.., ..,, ..,.,_ ,..,.,_..,Memyt f .nyl krtnne , .„ ,.,. ., .„, „ , , , .,, ,,. ,., , ..,„.,., , „

Ps"vtr>*SelfrV'.** . „ , _ , .,..,. , ___ .Tr...

S'l""" „-, , .,, _ .,..„...,,,

Tn»«ph«r,» _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .......

9 t. S.Tnr nr ph.nnl

S.4.4-TP (S.-K..V) - _ , - - „ - , „ - - . - ,...,..,.,._\«ny( rMnnrta _

CAS No.<

7440-3S-27440-39-3

71-43-27440-43-8

5ft-23-557-74-9

106-60-767-6«-3

7440-47-3S$-4«-7

10&-35-410..-44-5

B4-7&-7106-46-7107-06-275-35—4

121-14^272-20-876-44-e

110-74-167-68-367-72-1

7439-62-1SB-69-9

7439-97-C72-43-S76-63-398-95-387-e6-S

110-B6-17782-49 27440-22-4

127-1&-4B001-35-2

78-01-695-«f-«se-oe-283-72-17&-01-*

l *<mB/U

0051.00,0050.010.0050.0003I0.060.0522220.10.0750.0050.0070.00050.03020.000080.00320.0050.03O.C50.0040.0020.120.0210.040.010.05O.OD70.095O.OC540.020.01

• 0.002

Regjiaioryhrve' (mj'L)

50100,0

051.005003

100.0£050

• 2DO 0 •« 200.0 ••2000 ••2000 •

10,07 50.50.7

•0.130.020008

•0,130.53.0£.00,40.2

10.020CO

2,0*1000 •• 5 0 ^; o5.00.7

• 0.505

400.0 »2.0 •1.0OS

1 H«2JT3».-t wesie numb*..1 ChamiM! abstract; tetvtst numbe-.* OuanOixbon bmi a greater man r« calculated r»9Jlatcxy level. 7h< gumnAstsn Rnr therefore becomes UK rpodatary level.* n o-. nv, ani p-aesoJ concentrations cannot do amtrarmatai, trte totaJ cr*iol (OS2S) eoncar.!.-ali3n u us«C. Tr* regjuuvy level tor toul cresol is 200 mg/i.

The regulatory levels reflectedifications to some chronic toxjcityTerence levels since the original•oposai. EPA has revised some of theaximuffi Contaniinant Levels, Risk->ecific Doses, and Reference Doses tofleet new data and better methods. Insponse to comments received. EPAs decided not to apportion reference>ses of noncarcinogens to account foriltiple routes of exposure, a* wasiginaUy proposed (51 FR 21648). See:Uoa IILC for further discussion of

^mmenU.on apportionment and theency'* reasons for not includingportionment of reference doses in the

J Today's rule also promulgatesto replace the EP. The TCLPs in improvement over the EPmore accurately addresses

leaching potential for use in evaluatingwastes containing organic constituents,and also corrects several minortechnical deficiencies in the original EP.The version of the TCLP prooulgatedtoday reflects additional improvementsand modifications made to the TCLPsince the original proposal The TCLPpromulgated today will also replace theearlier version of the TCLP promulgatedas part of the land disposal restrictionsprogram.

Today's rule incorporates a schedulefor compliance that classifies theuniverse of potentially affected TCwaste handlers into two groups: (1) Allgenerators of greater than 100 kg/monthand less than 1,000 kg/month ofhazardous waste (small-quantitygenerators) must come into compliance

with the subtitle C requirements formanagement of their TC waste within 1yean and (2) all generators of 1,000 kg/month or more of hazardous waste arerequired to comply with all subtitle Crequirements for TC wastes within 6months. The phased schedule forcompliance is further discussed insection V.

Wastes identified as hazardous underthe Toxicity Characteristic will alsobecome hazardous substances undersection 101(14) of the ComprehensiveEnvironmental Response.Compensation, and Liability Act of I960(CERCLA), as amended. Today's ruleamends the list of reportable quantities(RQs) in 40 CFR part 302 by addingappropriate values for each of the new25 TC toxicanti. All of the newlv-

f l R 3 0 0 8 i 2







D. Date of Request:_____________

E. Site Name; AIW FRANK. CHESTER COUNTY. PA

Please provide below description of your request for SpecialAnalytical Services under the Contract Laboratory Program. Inorder to most efficiently obtain laboratory capability for yourrequest, please address the following considerations, ifapplicable. Incomplete information may result in a' delay in theprocessing of your request. Please continue response on additionalsheets, or attach supplementary information as needed.


Extraction of 6 soil samples by the TCLP Extraction methodwith the extracts being analyzed for the TCLP Metals by the3/90 CLP Inorganic SOW. See Attachment 1 for the full list ofTCLP metals .


6 low/medium concentration soil samples and 2 rinsate blanks. to be subjected to the TCLP extraction procedure and theextracts analyzed for TCLP metals. See Attachment 1 for thefull list of TCLP metals.


RI/FS - ARCS IIFT


HR3008I3

Estimated date(s) of collection:

To be determined.

Estimated date(s) and method of shipment:

To be determined.






TCLP Metals Analysis - 3/90 CLP Inorganic SOW

TCLP results are to be reported in ug/L.

8. Special technical instructions (if outside protocolrequirements, specify compound names, CAS numbers, detectionlimits, etc.):


All raw data. Deliverables as per the CLP SOWs. In addition,copies of TCLP extraction log book, signed and dated copy ofchain-of-custody documentation, copies of air bill confirmingsample receipt, and SAS Request Form are also required. TCLPextraction must be indicated on the Form I's.


Laboratory must comply with CSF requirements as specifiedin the 3/90 SOW. Laboratory will be responsible for thedisposal of all sample remnants and extracts.



flR3008U



TCLP Metals As per 3/90 CLP SOW As per 3/90 CLP SOW


Audits Required_____Frequency of Audits (Percent or Concentration)


With the following deviation:

Spike one TCLP leachate with all of the TCLP regulatedmetals. Provide all recovery data but do not performrecovery corrections.




Gregory L. Zimmerman - NUS Corporation - (412) 788-1080,June 6, 1991; revised September 5, 1991.


Please return this request to the Sample Management Office as soonas possible to expedite processing of your request for SpecialAnalytical Services. Should you have any questions or need anyassistance, please contact your local Regional representative atthe Sample Management Office. &

RR3QQ815

/j04 Federal Register / Vol. 55, No. 61 / Thursday. March 29, 1990 / Rules and Regulations

calculated regulatory level (i.e.. thechronic toxicity reference levelmultiplied by the DAF) it below theanalytical quanutation limit the

quantitaiion limit it the final regulator)'level. Note that the lift of constituent! inTable 112 contains the 14 constituentscurrently regulated under the existing

EPTC As specified in today's rule, theseconstituents will continue to beregulated at their current levels.

H.2.—TOXICTTY CHARACTERISTIC CONSTITUENTS AND REGULATORY LEVELS—— . ——— — — —

EPA HW No '

D00<D005D018O006O019D0?0002!0022D007D023D024D0250026O016 .D0270026DC29D030D012D031D03200330034oooa3013D309X>14X335X>36»37»3AOIOOil039015040041 . - -CX2 •3t7X3

Constituent (mg/L)

v»~-BinumBtrutne ——————————————————————————————— —— •C^dfTtttVTI •-- •••••••HI i i • ii JhnCarbon letncWonde ._ ... .... .. — _. — — .Otfo'diOf ' • —

nvCr«ioi...r5.jrjJfc*J»h«a,....-.tC,?...S:L.l.. ..,„.„ ,., „ ,„. ,. ......,„_,__...

2 4.Q . . . _..._ ... ..... ... . _ .. _ .. .

1 2»Dicruoroethar>e . „ ....... . . *. _ ....

2.4.DirulrolOluene ............_ _ .«.«.«... _________ . __ , ___ . _ .. _ •

Htplachlfy (inrl rts hyflroxirt^) , ..,.._......, —— . —— _ —— . — ...

Heracnlorc-1 3-buuidien« .. _ _.._.. ....i .. ... ............. .... . ..... ...... ._......

LM'I . , - , , , - - -Lmdant, .............. ................. ___ ..........Me/cury -, ,,,. , .,,.. .. ...... n...... ...,..,..,,. ,.-»• —

U«!hy( .tnyf kelBM ........ .... _. .... ..

PyndiDf ' .1 >nlervurr, —————————————————————————— ... ————— --...-.

P fi-Triehlrtrftphonnt _ __ _ . .._..., , ,,,!., , ...........?,J,iTP(S.k,.v). , . . . . , ,. ,. _______ .Vinyl ehfcvHe

CAS NO'

7440-38-27440-39-3

71-43-27440-43-9

56-23-557-74-9

108-90-767-66-3

7440-47-365^481-7

105-35-4106-44-5

94-75-7106-46-7107-06-275-35-4

121-14-272-20-876-u-e

110-74-187-68-367-72-1

7439-62- 158-69-9

7439-97-C72-43-576-93-398-95-387-86-5

110-86-17782-49 27440-22-4127-18-4

B 001 -35-279-01-685-95-486-06-293-72-175-01-<

Qvpnic lo«x*y rtvtnctt*r*(mg>L)

0051 00.0050,010.0050.000310.060.052222010,0750.0050.0070.00050,00020.000080.00020.0050,03O.C50.0040.0020.120.0210.040.010.050.0070.005O.OC54O.C2

. 0.010.002

~ — "Reguliio'Y

leve1 Imjj'l)

501000

051.0O S003

1000605,0

• 200 0 •• 200,0 ••2000 *' 200 0 •

1007 S0,50.7

'0.130.020008

•0.130,53,05.00.4P 9

10.02000

2.0*10C.O *•5.0 *

:.o5,00.7

' 0.50.5

400.0 »2.0 •1.00.2

1 Hazardous wesie number.' Chemical abstracts service numbe'.' OuanbiitDon hmit is greater tnasi tr« calculated regulatory level. The guannsban Grrrf therefore becomes th* reoulatary level.' H c-, m-. and p-cresoJ concentrations cannot &e drtleranbatac-. me toll.' c/esol (OG25) concont-a'.ian is uaet. Th« re;jtalc<rejjtalory l«v«l tor loUl creso! u 200 mg/l.

The regulatorj- levels reflectDdifications to some chronic toxicityTerence levels since the originaloposai. EPA has revised some of theiximum Contaminant Levels. Risk-ecific Doses, and Reference Doses toled new data and better methods. Inponse to comments received, EPA; decided not to apportion reference;es of noncarcinogens to account forItiple routes of exposure, as wasynally proposed (51 FR 21648). Seetioa I1LC for further discussion ofimeaU on apportionment and themcy*s reasons for not includingortionment of reference doses in the1 rule. Today's rale also promulgatesTCLP to replace the EP. The TCLPesents an improvement over the EPiat it more accurately addresses

leaching potential for use in evaluatingwastes containing organic constituents,and also corrects several minortechnical deficiencies in the original EP.The version of the TCLP promulgatedtoday reflects additional improvementsand modifications made to the TCLPsince the original proposal The TCLPpromulgated today v/ill also replace theearlier version of the TCLP promulgatedas part of the land disposal restrictionsprogram.

Today's rule incorporates a schedulefor compliance that classifies theuniverse of potentially affected TCwaste handlers into two groups: fl) Allgenerators of greater than 100 kg/monthand less than 1,000 kg/month ofImardous waste fsmall-quantitygenerators) must come into compliance

with the subtitle C requirements formanagement of their TC \vaste within 1yean and (2) all generators of 1,000 kg/month or more of hazardous waste arerequired to comply with all subtitle Crequirements for TC wastes within 6months. The phased schedule forcompliance is further discussed insection V,

Wastes identified as hazardous underthe Toxicity Characteristic will alsobecome hazardous substances undersection 101(14) of the ComprehensiveEnvironmental Response,Compensation, and Liability Act of 1980(CERCLA}, as amended. Today's ruisamends the list of reporlable quantities(RQs) in 40 CFR part 302 by addingappropriate values for each of the new25 TC toxicants. AH of the newlv-

f l 'R3008!6

nU.S. ENVIRONMENTAL PROTECTION AGENCY SAS NUMBERCLP SAMPLE MANAGEMENT OFFICEP.O. BOX 818 - ALEXANDRIA, VIRGINIA 22313PHONE: 703/557-2490 - FTS/557-2490



A. EPA Region/ClientiEPA-REGION III-ARCS III


c. Telephone Number; (301) 266-9180

D. Date of Request:.__________

E. Site Name; AIW FRANK, CHESTER COUNTY, PA



Analysis of 6 soil samples for TOG and Cation ExchangeCapacity (CEC) by the methods listed in Item 7. Sodiumdetermination as per 3/90 Inorganic CLP SOW.


6 low concentration soil samples for the above analysis.


RI/FS - ARCS III



To be determined.


To be determined.


•


TOG samples must be analyzed within 28 days of VTSR for eachsample. Written results are due within 35 days of the receiptof the last sample.


TOG - Method 29.3.5.2 from "Methods of Soil Analysis",Agronomy No. 9.

CEC - SW846 - 9081

The methods are attached.

8. Special technical instructions (if outside protocolrequirements, specify compound names/ CAS numbers,detection limits/ etc.):

For TOG, perform duplicate analysis on one of every 10samples or fractions thereof. Standardize the instrumentaccording to manufacturer's instructions.

9. Analytical results required (if known/ specify format for datasheets/ QA/QC reports, Chain-of-Custody documentation, etc.)-if not completed, format of results will be left to programdiscretion:

Raw data, calculations, data sheets, blank results, duplicateresults, signed and dated chain-of-custody documentation, SASpacking list, copy of the air bill confirming sample receipt,SAS packing list, and SAS request form. In addition, for theTOG narrative, include a description of process utilized anddescription of problems encountered. Also include analystlogbook pages, and weights and volumes used.

10. other (use additional sheets or attach supplementaryinformation/ as needed):

Laboratory must comply with purge file requirements.Contact SMO for details.


Jeff Orient - NUS Corporation(412)-788-1080. AR3QQ8 i 8


Parameter________Detection Limit______(+/-% or Concentration)

TOG (soil) 10 mg/kg ± 30%

TOC (water) 1 ppm +20%

CEC 1 meq/100 g ± 20%

Sodium as per CLP SOW as per CLP SOW



Blanks (TOC) 1/10 Below detection limit

Duplicate (TOC) 1/10 ±30% RPDSoil TOC certified standard 1/10 95% CI - report true values

Balance check with NBS Class "S" weights - report reults.

Sodium as per CLP SOW as per CLP SOW

CEC method blank 1 blank as per < method det. limitSection 8.2 of 9081

14. Action Required if Limits are Exceeded:Re-analyze samples once more and report both sets of data andall associated QC.


Gregory L. Zimmerman - NUS Corporation - (412) 788-1080.June 6, 1991.



HR3QQ819

tBON AND ORGANIC MATTER 29-3 ORGANIC CARBON 565

•s of this reagent adds 6 meq5°7o CaCOj in a 2-g soil sam-: present to ensure completerig > 3 ml of the 2N reagentjquivalent, it is preferable toeagent.

:OMBUSTION

>ecial apparatus listed in sec-

o: Bubble SO2 through dis-tained. Keep the bottle well

imple that passes through aof known water content to a:viously ignited and cooled.SOj solution. After severaleaving the boat overnight in•llets. Repeat the treatmenti.: C by one of the dry corn-Report the C present in the

>il Extracts

J-2.3.3.1.

depending on the organic Cnd add 1 ml of the H2SO4-i boiling water, and direct athe liquid in the flask. Re-

or less. Add five or six glass:eed with the determination

29-3.4.4 COMMENTS

Drying of extracts is best accomplished in 100-ml flasks of the Kjeldahltype. A 2-liter beaker conveniently holds four flasks.

29-3.5 Rapid Dichromate Oxidation Techniques

29-3.5.1 INTRODUCTION AND PRINCIPLES

Schollenberber (1927) first proposed that the organic matter in soil maybe oxidized by treatment with a hot mixture of K2Cr2O7 and H2SO4 accord-ing to Eq. [9J.

2 Cr2O,2- + 3 C° + 16 H* = 4 CrJ* + 3 CO2 + 8 H2O. [9]

After the reaction, the excess Cr2(V is titrated with Fe(NH4)2(SO4)2«6H2O,and the Cr2O7

2~ reduced during the reaction with soil is assumed to beequivalent to the organic C present in the sample. It must be emphasizedthat all methods based on analysis of Cr2O7

2' remaining or Cr3* formed as-sume that C in soil organic matter has an average valence of zero. Althoughmost dichromate oxidation procedures described since the original Schol-lenberger method have involved chromic acid solutions or mixtures of con-centrated H2SO4 and aqueous K2Cr2O7 solutions (Table 29-3), the use ofother oxidants has been proposed. Degtijareff (1930) suggested that a mix-ture of H2O2 and chromic acid be used to oxidize organic matter. However,Walkley and Black (1934) conclusively established that the addition of H2O2to chromic acid procedures gave fictitiously high values for organic C be-cause H2O2 reduces Cr2CV~ in acid solution. Tinsley (1950) and Kalembasaand Jenkinson (1973) proposed that the chromic acid mixture used to oxi-dize organic C compounds be 9 and 4.5N, respectively, with respect toH3PO4. There is no evidence, however, to suggest that oxidation mixtures

Table 29-3. Digestion reagents used in various rapid dichromate methodsfor organic C determinations.

Digestion reagent concentrationMethod

Schollenberger<1927)Tyurin{1931)Walkley & Black (1934)Anne (1945)Tinsley (1950)Mebius (1960)Kalembasa & Jenkinson (1973)Nelson & Sommers (1975)Modified Mebius (described here)

K,Cr,0,t

0.350.400.330.160.400.2670.200.400.20

H.SO,—— N ———

3618252215201821.621.6

H.PO,

_--_9_5..-

t Based on Cr.O," + 14H' = 2Cr" + 7H.O + 6e'half reaction.

A R 3 Q 0 8 2 Q

566 CARBON AND ORGANIC MATTER

containing H,PO4 are more efficient in oxidizing organic matter comparedwith K2Cr2O7-H2SO4 mixtures. The oxidizing mixture used in most pro-posed methods is between 0.16 to 0.35^ in K2Cr2O, and 15 to 25N in H2SO4(Table 29-3). However, Tyurin (1931), Tinsley (1950), and Nelson andSommers (1975) used an aqueous H2SO4 mixture that was 0.4A^in K2Cr2O,,whereas Schollenberger (1927) used concentrated H2SO, (-36AO as the sol-vent for K2Cr2O,.

Schollenberger (1927) suggested that the soil-H2SO«-K2Cr2O7 mixturebe heated in a Pyrex test tube over a flame until the solution temperaturereached 175°C, at which time heating was discontinued. Later investigatorsrealized that the time and temperature of heating was critical and must bestandardized. Degtjareff (1930), Tyurin (1931), Schollenberger (1945), andJackson (1958) suggested that the soil-chromic acid mixtures should beheated in test tubes submerged in H2SO4 or oil baths for 10 min at 165°C, 5min at about 170°C, 5 min at 140°C, and 5 min at 155°C, respectively. Onthe other hand, Walkley and Black (1934) recommended that heat of dilu-tion of H2SO4 was satisfactory for oxidizing organic matter and that no ex-ternal heat was needed. More recently, other investigators have found thatan extended period of heating is required to obtain quantitative oxidationof organic C compounds by chromic acid (Anne, 1945; Tinsley, 1950;Mebius, I960; Kalembasa & Jenkinson, 1973). Tinsley proposed that a coldfinger condenser fitted on an Erlenmeyer flask be used to prevent loss ofwater during the heating period, whereas the other workers usedErlenmeyer flasks fitted with Liebig condensers. Heating time varied from20 min to 2 hours, and the temperature of heating (boiling point of acidsolution) was dependent on the H2SO4 concentration in the oxidation mix-ture. Recently, Nelson and Sommers (1975) proposed that soil-chromic acidmixtures be heated under reflux in Folin-Wu nonprotein N tubes placed inan Al block on a hot plate. Heating time and temperature recommendedwere 30 min and 150°C, respectively.

Diphenylamine was the first oxidation-reduction indicator used for thetitration of excess Cr2(V with Fe2* (Schollenberger, 1927, 1931, 1945; Alli-son, 1935). Later studies suggested that the diphenylamine endpoint couldbe improved by addition of H,PO4, NaF, or HF before titration (Schollen-berger, 1931, 1945; Walkley & Black, 1934), and these substances werewidely used in dichromate titrations. Peech et al. (1947) established thatbarium diphenylamine sulfonate in combination with HjPO4 was as effec-tive and more stable compared with diphenylamine and has been used as anindicator in other procedures (Tinsley, 1950). Jackson (1958) recommendedthat o-phenanthroline be used as an indicator in Cr*O7

2" titrations becausethe color change (formation of the complex with Fe2*) occurs at higheroxidation-reduction potential compared with diphenylamine. A mixture ofo-phenanthroline and H5PO4 is normally used to give a good endpoint;however, the indicator has been successfully used without HjPO4 addition.A problem with o-phenanthroline is that the indicator tends to be absorbedby some suspended soil materials, obscuring the color change at the end-point. Therefore, the diluted chromic acid-soil mixture is often passedthrough a fast filter paper on a Biichner funnel before titration. Simakov

29-3 ORGANIC CARBON

(1957) proposed that Af-prnCr2O7

2' titrations with FeJ

thranilic acid gives a very scurrently the indicator of ch

Other methods of titr;tors have been used to estimslight excess of Fe2* to thtitrate the Fe2* with KMnOcedure, the only reagent thaamounts of Fe2* and Cr2Oendpoint in the titration ofcurately by monitoring ttcalomel electrodes attache1973). The endpoint of thewith 0.02 ml of titrant.

The amounts of Cr;Cmatter may also be estimattion or centrifugation (Caused to determine the amovwith soil (Graham, 1948; l

Bolt, 1974; Gupta et al., ISquantitated at wavelengthlated to organic matter cor1948; Sims & Haby, 197!colorimeter to measure Crcentrifugation, thereby acuvette. In a comparison cthat determine Cr3*, Metscthe preferred procedure.

Dichromate methodsnot give complete oxidatioractive forms of organic C .found that on the averagecovered by the heat of dilution factor of 1.32 be used

Table 29-4. Correction factor:method as determin

Reference

Bremner & Jenkinson (1960s}Kalembasa & Jenkinson (1973)Orphanos(1973)RichteretaL(1973)Nelson & Sommers (1975)

:ARBON AND ORGANIC MATTERiizing organic matter compareding mixture used in most pro-:2Cr2O, and 15 to 257V in H2SO4nsley (1950), and Nelson andcture that was 0.4>Vin K2Cr2O7,-ated H2SO, (~36N) as the sol-

e soil~H2SO4-K2Cr2O7 mixtureuntil the solution temperature

,scontinued. Later investigatorsmating was critical and must be51), Schollenberger (1945), andomic acid mixtures should be>il baths for 10 min at 165° C, 5min at 155°C, respectively. Onecommended that heat of dilu-organic matter and that no ex-r investigators have found that> obtain quantitative oxidation

(Anne, 1945; Tinsley, 1950;). Tinsley proposed that a coldask be used to prevent loss ofas the other workers used;ers. Heating time varied fromheating (boiling point of acidntration in the oxidation mix-roposed that soil-chromic acidnonprotein N tubes placed in

nd temperature recommended

:duction indicator used for theberger, 1927, 1931, 1945; Alli-liphenylamine endpoint couldHF before titration (Schollen-), and these substances wereet al. (1947) established thation with H3PO4 was as effec-imine and has been used as anJackson (1958) recommended• in Cr2O7

2' titrations becausec with Fe2*) occurs at higherdiphenylamine. A mixture ofed to give a good endpoint;ised without HjPO. addition,idicator tends to be absorbedthe color change at the end-soil mixture is often passedicl before titration. Simakov

29-3 ORGANIC CARBON 567

(1957) proposed that Af-phenylanthranilic acid be used as an indicator inCr2O7

2' titrations with Fe2*. Mebius (1960) confirmed that W-phenylan-thranilic acid gives a very sharp and clean endpoint, and this compound iscurrently the indicator of choice for Cr2O7

l" titrations.Other methods of titration not involving oxidation-reduction indica-

tors have been used to estimate unreacted Cr2O72'. One approach is to add a

slight excess of Fe2* to the Cr2O,2"-H2SO4-soil mixture and then back-titrate the Fe2* with KMnO, (Smith & Weldon, 1941). In this titration pro-cedure, the only reagent that requires standardization is KMnOa if the sameamounts of Fe2* and Cr2O7

2" are added to both samples and blanks. Theendpoint in the titration of Cr2Or

2" with Fe2* may also be estimated very ac-curately by monitoring the oxidation-reduction potential with Pt andcalomel electrodes attached to a potentiometer (Raveh & Avnimelech,1973). The endpoint of the titration involves a voltage change of -400 mVwith0.02mloftitrant.

The amounts.of Cr2O72~ remaining after reaction with soil organic

matter may also be estimated by colorimetry after removal of soil by filtra-tion or centrifugation (Carolan, 1948). Conversely, colorimetry may beused to determine the amounts of Cr3* formed from the reaction of Cr2O7

2'with soil (Graham, 1948; Sinha & Prasad, 1970; Sims & Haby, 1971; DeBolt, 1974; Gupta et al., 1975; Baker, 1976). The green color due to Cr>* isquantitated at wavelength of 600 nm, and the absorbance is normally re-lated to organic matter concentration in soil by a standard curve (Graham,1948; Sims & Haby, 1971; De Bolt, 1974). Baker (1976) used a probecolorimeter to measure Cr3* absorbance directly in the reaction vessel aftercentrifugation, thereby avoiding a transfer into a spectrophotometercuvette. In a comparison of the methods that quantitate Cr2O7

2" and thosethat determine Cr3*, Metson (1956) indicated that measurement of Cr3* isthe preferred procedure.

Dichromate methods that use heat of dilution or minimal heating donot give complete oxidation of organic compounds in soil although the mostactive forms of organic C are converted to CO2. Walkley and Black (1934)found that on the average about 76% of the organic C in 20 soils was re-covered by the heat of dilution procedure, and they proposed that a correc-tion factor of 1.32 be used to account for unrecovered organic C. However,

Table 29-4. Correction factors for organic C not recovered by the Walkley and Black______method as determined for surface soils by various investigators.______

Number of Organic C recovery Averagesoils ——————————— correction

Reference studied Range Average factor

Bremner & Jenkinson (1960a)Kalembasa & Jenkinson (1973)Orphanos (1973)Richter eta! (1973)Nelson & Sommers (1975)

152212

•1210

57-9246-8069-7979-8744-88

8477758379

1.191.301.331.201.27

R R 3 0 0 8 2 2


the actual recoveries of organic C from the soils tested varied from 60 to86%. Allison (1960) reviewed available information on the recovery of or-ganic C in a wide variety of soils by the Walkley and Black procedure andshowed that the average recovery with different groups of soils varied from63 to 86% and that the correction factor varied from 1.16 to 1.59. Table29-4 gives data on the correction factor found to be required for theWalkley and Black procedure in investigations carried out during recentyears. Recoveries of organic C by the Walkley and Black technique werehighly variable, and the correction factor appropriate for individual soilsvaried from 1.09 to 2.27. The average correction factor appropriate for agroup of soils varied from 1.19 to 1.33. The above clearly indicate thatCr2O72"-H2SO4 methods that involve minimal heating give variable recoveryof organic C from soils. An average correction factor found for a group ofsoils may be applicable to the "average" soil in the group but will give er-roneous values for many soils in the group. Therefore, procedures such asthe Walkley and Black should be considered to give approximate or semi-quantitative estimates of organic C in soil because of the lack of an appro-priate correction factor for each soil analyzed. If an experimentally de-termined correction factor is not available for a particular group of soils,the use of 1.3 as the factor appears most reasonable over a range of soils.Methods that involve extensive heating, such as those of Tinsley (1950) orMebius (1960), do not require a correction factor because all of the organicC in the soil is oxidized to CO2. However, methods that involve minimalheating (e.g., Schollenberger, 1927) require a small correction factor (e.g.,1.15) to account for unreacted organic C.

The rapid dichromate methods are subject to interferences by certainsoil constituents that lead to spurious results in some soils (Walkley, 1947).Chloride, ferrous iron, and higher oxides of manganese have been shown toundergo oxidation-reduction reactions in chromic acid mixtures leading toincorrect values for organic C. The presence of significant amounts of Fe2*or Cl" in soil will lead to a positive error, whereas MnO2 will result in anegative error and low values for organic C.

Chloride interferes with dichromate methods through the formation ofchromyl chloride, as indicated in Eq. [4], which results in consumption ofCr2O7

2". Chloride interference may be eliminated by washing the soil free ofCl" before analysis or by precipitating the Cl" as AgCl by addition ofAg2SO« to the digestion acid (Walkley, 1947; Quinn & Salomon, 1964). Al-ternatively, Walkley (1947) found that Eq. [10] may be used to correct or-ganic C values for soils having a Cl/C ratio of s5:1:

Organic C in soil (%) = (Apparent % C in soil) - (% C1V12). [10]

When present in soil, Fe2* will be oxidized to FeJ* by Cr2O72", as indi-

cated in Eq. [11], resulting in a positive error in the analysis, i.e., givinghigh values for organic C content:

CrjO,1' + 6Fe2* + 14H* = 2Cra* -I- 6Fe3* + 7H2O. [HI

29-3 ORGANIC CARBON

Appreciable Fe2* may be presetresult when dichromate methoc(Lee, 1939). However, Walkley.duced soils before analysis resuldetermination of the organic Cwell-aerated soils are so small rtthat no detectable interferencesamples may also lead to posiTherefore, care should be takenor steel equipment before analys

The higher oxides of Mn (kdizable substances when heated

2MnO2 + C° 4- 8

Therefore, any reactive MnO2 pare analyzed by dichromate tec!amounts of MnOz and other teluded that in most soils the quasmall because only the freshlyreactions. Even in highly mang;MnO2 present is able to compecompounds. Therefore, interferous error in the vast majority of

Other problems associatedtions about the average oxidatioweight of C) and recovery of hijAll dichromate methods assum<oxidation state of zero and an etreacted with dichromate accordinconducted to evaluate this assuimethods using extensive heatingtained with wet or dry combusigests that this assumption is resinvolve little or no external heapresent in carbonized materialssoot). For example, Walkley (19od recovered only 2 to 11 % of tdetailed study, Bremner and JerBlack method gave low recovematerials, whereas methods invlenberger and Tinsley gave subsorganic C from such materialsmethods cannot be used to quansoils or to discriminate betweenganic matter because organic Cthe chromic acid mixture. There

A R 3 0 Q 8 2 3

:ARBON AND ORGANIC MATTERe soils tested varied from 60 toormation on the recovery of or-alkley and Black procedure andrent groups of soils varied from•aried from 1.16 to 1.59. Tablefound to be required for the

tions carried out during recentkley and Black technique wereappropriate for individual soilsection factor appropriate for aThe above clearly indicate thatal heating give variable recoveryion factor found for a group of>il in the group but will give er-Therefore; procedures such as

d to give approximate or semi-ecause of the lack of an appro-ved. If an experimentally de-for a particular group of soils,asonable over a range of soils.h as those of Tinsley (1950) oractor because all of the organicmethods that involve minimala small correction factor (e.g.,

ject to interferences by certainin some soils (Walkley, 1947).

manganese have been shown toromic acid mixtures leading toof significant amounts of Fe2*

whereas MnO2 will result in a

hods through the formation oflich results in consumption ofited by washing the soil free ofCl' as AgCl by addition ofQuinn & Salomon, 1964). Al-

10] may be used to correct or-

3insoil)-(%ClY12). [10]

ed to Fe3* by CrzOj2', as indi-Dr in the analysis, i.e., giving

29-3 ORGANIC CARBON 569

6Fe3* + 7H2O. [11]

Appreciable Fe2* may be present in highly reduced soils, and errors mayresult when dichromate methods are applied to such soils before drying(Lee, 1939). However, Walkley (1947) found that thorough air-drying of re-duced soils before analysis resulted in oxidation of Fe2* to Fe3* and accuratedetermination of the organic C present. The amounts of Fe2* present inwell-aerated soils are so small relative to the amounts of organic C presentthat no detectable interference is likely. Metallic iron (Fe°) present in soilsamples may also lead to positive interferences in dichromate methods.Therefore, care should be taken to ensure that soils are not ground with Feor steel equipment before analysis.

The higher oxides of Mn (largely MnO2) compete with Cr2O72" for oxi-

dizable substances when heated in an acid medium according to Eq. [12].

2MnO2 + C° + 8H* = CO2 + Mn2* + 4H2O. [12]

Therefore, any reactive MnO2 present will give a negative error when soilsare analyzed by dichromate techniques. Although soils contain substantialamounts of MnO2 and other higher oxides of Mn, Walkley (1947) con-cluded that in most soils the quantity of reactive (reducible) oxides of Mn issmall because only the freshly precipitated MnO2 will take part in redoxreactions. Even in highly manganiferous soils, only a small fraction of theMnO2 present is able to compete with Cr2(V for oxidation of organic Ccompounds. Therefore, interference from MnO2 is not thought to be a seri-ous error in the vast majority of soils.

Other problems associated with dichromate methods involve assump-tions about the average oxidation state of organic C in soils (i.e., equivalentweight of C) and recovery of highly reduced forms of organic C from soils.All dichromate methods assume that the organic C in soil has an averageoxidation state of zero and an equivalent weight of 3 g per equivalent whenreacted with dichromate according to Eq. [9] even though no studies have beenconducted to evaluate this assumption. However, the fact that dichromatemethods using extensive heating give organic C values similar to those ob-tained with wet or dry combustion where CO2 is determined directly sug-gests that this assumption is reasonably correct. Dichromate methods thatinvolve little or no external heating give very poor recovery of organic Cpresent in carbonized materials (e.g., charcoal, graphite, coal, coke, andsoot). For example, Walkley (1947) found that the Walkley and Black meth-od recovered only 2 to 11 % of the organic C present in such materials. In adetailed study, Bremner and Jenkinson (1960b) found that the Walkley andBlack method gave low recovery (<36%) of organic C from carbonizedmaterials, whereas methods involving external heat such as those of Schol-lenberger and Tinsley gave substantial (55-110%) and variable recovery oforganic C from such materials. The authors concluded that dichromatemethods cannot be used to quantitatively recover carbonized materials fromsoils or to discriminate between C in carbonized materials and C in soil or-ganic matter because organic C recovery varied with the time of heating ofthe chromic acid mixture. Therefore, unreliable results for organic C will be


obtained if dichromate methods are applied to soils containing significantamounts of carbonized materials. Dry combustion methods are most appro-priate for soils containing large amounts of elemental C.

29-3.5.2 WALKLEY-BLACK PROCEDURE (Walkley, 1946; Peech et al., 1947;Greweling&Peech, 1960)

29-3.5.2.1 Reagents.1. Potassium dichromate (K2Cr2O7), IN: Dissolve 49.04 g of reagent-grade

K2Cr2O7 (dried at 105°C) in water, and dilute the solution to a volume of1,000ml.

2. Sulfuric acid (HUSO,), concentrated (not less than 96%): If Cl" is presentin soil, add Ag2SO4 to the acid at the rate of 15 g/liter.

3. Phosphoric acid (H,PO4), concentrated.4. o-Phenanthroline-ferrous complex, 0.025A/: Dissolve 14.85 g of o-phen-

anthroline monohydrate and 6.95 g of ferrous sulfate heptahydrate(FeSO4«7H2O) in water. Dilute the solution to a volume of 1,000 ml. Theo-phenanthroline-ferrous complex is available under the name of Fer-roin from the G. Frederick Smith Chemical Co. (Columbus, Ohio).

5. Barium diphenylamine sulfonate: Prepare a 0.16% aqueous solution.This reagent is an optional substitute for no. 4.

6. Ferrous sulfate heptahydrate (FeSO4«7H2O) solution, Q.5N: Dissolve140 g of reagent-grade FeSO4«7H2O in water, add 15 ml of cone sulfuricacid (H2SO«), cool the solution, and dilute it to a volume of 1,000 ml.Standardize this reagent daily by titrating it against 10 ml of IN potas-sium dichromate (K2Cr2O7), as described below.

29-3.5.2.2 Procedure. Grind the soil to pass through a 0.5-mm sieve,avoiding Fe or steel mortars. Transfer a weighed sample, containing 10 to25 mg of organic C, but not in excess of 10 g of soil, into a 500-ml wide-mouth Erlenmeyer flask. Add 10 ml of IN K2Cr2O7, and swirl the flaskgently to disperse the soil in the solution. Then rapidly add 20 ml of coneH2SO4, directing the stream into the suspension. Immediately swirl the flaskgently until soil and reagents are mixed, then more vigorously for a total of1 min. Allow the flask to stand on a sheet of asbestos for about 30 min.Then add 200 ml of water to the flask, and filter the suspension if experi-ence shows that the endpoint of the titration cannot otherwise be clearly dis-cerned. Add 3 to 4 drops of o-phenanthroline indicator, and titrate the solu-tion with 0.5A/TeSO4. As the endpoint is approached, the solution takes ona greenish cast and then changes to a dark green. At this point, add theferrous sulfate heptahydrate drop by drop until the color changes sharplyfrom blue to red (maroon color in reflected light against a white back-ground). Make a blank determination in the same manner, but without soil,to standardize the Cr2(V~. Repeat the determination with less soil if >75%of the dichromate is reduced.

Calculate the results according to the following formula, using a cor-rection factor/ = 1.30 or a more suitable value found experimentally:

29-3 ORGANIC CARBON

(meq iOrganic C, <7b = -——

29-3.5.2.3 Commentstitrant for excess Cr2O7

2~ inThe Smith and Weldon (1941Cr2O7

2' with Fe2*, and subsesolution may also be used tcreduction indicators that ha\diphenylamine sulfonate anCr2O7

2" reduced to CrJ* byestimated colorimetrically.

29-3.5.3 MODIFIED MEBIU

29-3.5.3.1 Special Apr1. Erlenmeyer flasks (125 i

ground-glass joints (Corni2. West condensers (30 cm)

glass joints at the lower en3. Electric hot plate extract

dividual rheostat controlsMulti-Unit Extraction He;

29-3.5.3.2 Reagents.1. Potassium dichromate sol

K2Cr2O7 (oven-dry) in 2002. Sulfuric acid (H2SO4), con3. Ferrous ammonium suli

6H,OJ, 0.2N: Dissolve 7?cone H2SO4, and dilute toized daily because of slow

4. Indicator solution: Dissol0.107 g of sodium carbona

29-3.5.3.3 Procedure.containing not greater than Jflask. Add exactly 10 ml of 0.(H2SO4 may be added by burand place on a preheated electfive soil samples to be heatecblanks are unheated mixturesH2SO4) for each day that arFe(NH4)2(SO4)2«6HjO soluti<blank. Gently boil each sampbetween the hot plate and boito cool for about 15 min, ar

S R 3 0 0 8 2 5

I AND ORGANIC MATTER

Is containing significantnethods are most appro-alC.

v, 194<5;Peechetal., 1947;

19.04 g of reagent-gradesolution to a volume of

i 96%): If cr is presentliter.

solve 14.85 g of o-phen-s sulfate heptahydrateolumeof 1,000ml. Thender the name of Fer-3olumbus, Ohio).6% aqueous solution.

lution, 0.57V: Dissolve1 15 ml of cone sulfurica volume of 1,000 ml.ist 10 ml of IN potas-

rough a 0.5-mm sieve,nple, containing 10 to1, into a 500-ml wide-•7, and swirl the flaskily add 20 ml of coneediateiy swirl the flasklorously for a total ofos for about 30 min.suspension if experi-

herwise be clearly dis-r, and titrate the solu-the solution takes ont this point, add the:olor changes sharplygainst a white back-ner, but without soil,'ith less soil if > 75%

brmula, using a cor-sxperimentally:

29-3 ORGANIC CARBON

Organic C, % = (meqK2Cr2O, - meq FeSQ4)(0.003)(100)g water-free soil

571

x/. [13]

29-3.5.2.3 Comments. Ferrous ammonium sulfate is also a suitabletitrant for excess Cr2O7

2' in conjunction with the Walkley-Black method.The Smith and Weldon (1941) modification involving complete reduction ofCr2O7

J~ with Fe2*, and subsequent back-titration of excess Fe2* with MnOrsolution may also be used to estimate unreacted Cr2O7

2~. Other oxidation-reduction indicators that have provided satisfactory results include bariumdiphenylamine sulfonate and /V-phenylanthranilic acid. The amounts ofCr2O7

J~ reduced to Cr3* by reaction with soil organic matter may also beestimated colorimetrically.

29-3.5.3 MODIFIED MEBIUS PROCEDURE

29-3.5.3.1 Special Apparatus.1. Erlenmeyer flasks (125 ml) fitted with female standard-taper 24/40

ground-glass joints (Corning 5000 or Kimble 26510).2. West condensers (30 cm) fitted with male standard-taper 24/40 ground-

glass joints at the lower end (Corning 2800 or Kimble 18190).3. Electric hot plate extraction unit (six plates per unit) fitted with in-

dividual rheostat controls (Labconco 60300, Precision 65500, Lab-LineMulti-Unit Extraction Heater, or equivalent).

29-3.5.3.2 Reagents.1. Potassium dichromate solution (K2Cr2O,), 0.5N: Dissolve 24.5125 g of

K2Cr2O7 (oven-dry) in 200 ml of deionized water, and dilute to 1 liter.2. Sulfuric acid (H2SO<), concentrated, not less than 96%.3. Ferrous ammonium sulfate hexahydrate solution [Fe(NH4)2(SO4)2«

6H2O], 0.2N: Dissolve 78.390 g of Fe(NH4)2(SO4)2«6H2O in 50 ml ofcone H2SO4, and dilute to 1 liter with deionized water (must be standard-ized daily because of slow oxidation).

4. Indicator solution: Dissolve 0.100 g of /V-phenylanthranilic acid and0.107 g of sodium carbonate (Na2CO3) in 100 ml of water.

29-3.5.3.3 Procedure. Weigh an amount of < 100-mesh soil (< 0.5 g)containing not greater than 8 mg of organic C into a 125-ml Erlenmeyerflask. Add exactly 10 ml of 0.5N K2Cr2O, solution and 15 ml of cone H2SO4(H2SO4 may be added by burette). Attach the flask to the West condenser,and place on a preheated electric hot plate. Include a blank in each group offive soil samples to be heated and at least two unboiled blanks (unboiledblanks are unheated mixtures of 10 ml of Q.SN K2Cr2O7 and 15 ml of coneH2SO4) for each day that analyses are performed. The normality of theFe(NH4)2(SO4)2-6H2O solution is determined by titrating the unboiledblank. Gently boil each sample for 30 min, and then insert an asbestos padbetween the hot plate and bottom of the Erlenmeyer flask. Allow the flaskto cool for about 15 min, and rinse the inside of the condenser with de-

S R 3 0 0 8 2 6

METHOD 9081

CATION-EXCHANGE CAPACITY OF SOILS (SODIUM ACETATE)

1.0 SCOPE AND APPLICATION

1.1 Method 9081 1s applicable to most soils, Including calcareous andnoncalcareous soils. The method of cation-exchange capacity by summation(Chapman, 1965, p. 900; see Paragraph 10.1) should be employed for distinctlyadd soils.

2.0 SUMMARY OF METHOD

2.1 The soil sample 1s mixed with an excess of sodium acetate solution,resulting 1n an exchange of the added sodium cations for the matrix cations.Subsequently, the sample 1s washed with 1 sop ropy 1 alcohol. An ammoniumacetate solution 1s then added, which replaces the adsorbed sodium withammonium. The concentration of displaced sodium 1s then determined by atomicabsorption, emission spectroscopy, or an equivalent means.

3.0 INTERFERENCES

3.1 Interferences can occur during analysis of the extract for sodiumcontent. Thoroughly Investigate the chosen analytical method for potentialInterferences.

4.0 APPARATUS AND MATERIALS

4.1 Centrifuge tube and stopper; 50-mL, round-bottom, narrow neck.

4.2 Mechanical shaker.4.3 Volumetric flask; 100-mL.

5.0 REAGENTS

5.1 Sodium acetate (NaOAc), 1.0 N: Dissolve 136 g of NaC^H^C^-S^O 1nwater and dilute 1t to 1,000 mL. The pH of this solution should be 8.2. Ifneeded, add a few drops of acetic add or NaOH solution to bring the reactionof the solution to pH 8.2.

5.2 Ammonium acetate (NH40Ac), 1 N; Dilute 114 mL of glacial aceticacid (99. 5X) with water to a volume of approximately 1 liter. Then add 138 mLof concentrated ammonium hydroxide (NH40H) and add water to obtain a volume ofabout 1,980 mL. Check the pH of the resulting solution, add more NH40H, asneeded, to obtain a pH of 7, and dilute the solution to a volume of 2 literswith water.

9081 - 1Revision 0Date September 1986

HR300827

5.3 Isopropyl alcohol; 99X.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 All samples must be collected using a sampling plan that addressesthe considerations discussed 1n Chapter Nine of this manual.

7.0 PROCEDURE

7.1 Weigh 4 g of medium- or flne-textured soil or 6 g of coarse-texturedsoil and transfer the sample to a 50-mL, round-bottom, narrow-neck centrifugetube. (A fine soil has >50% of the particles <0.074 mm, medium soil has >50X}0.425 mm, while a coarse soil has more than 50X of Its particles >2 mm.

7.2 Add 33 mL of 1.0 N NaOAc solution, stopper the tube, shake 1t 1n amechanical shaker for 5 m1n, and centrifuge 1t until the supernatant liquid 1sclear.

7.3 Decant the liquid, and repeat Paragraph 7.2 three more times.

7.4 Add 33 mL of 99% Isopropyl alcohol, stopper the tube, shake 1t 1n amechanical shaker for 5 m1n, and centrifuge 1t until the supernatant liquid 1sclear.

7.5 Repeat the procedure described 1n Paragraph 7.4 two more times.

7.6 Add 33 mL of NfyOAc solution, stopper the tube, shake 1t 1n amechanical shaker for 5 m1n, and centrifuge It until the supernatant liquid 1sclear. Decant the washing Into a 100-mL volumetric flask.

7.7 Repeat the procedure described 1n Paragraph 7.6 two more times.

7.8 Dilute the combined washing to the 100-mL mark with ammonium acetatesolution and determine the sodium concentration by atomic absorption, emissionspectroscopy, or an equivalent method.

8.0 QUALITY CONTROL

8.1 All quality control data should be maintained and available for easyreference or Inspection.

8.2 Employ a minimum of one blank per sample batch to determine 1fcontamination or any memory effects are occurring.

8.3 Materials of known cation-exchange capacity must be routinelyanalyzed.

9081 - 2RevisionDate September 1986

9.0 METHOD PERFORMANCE

9.1 No data provided.

10.0 REFERENCES

10.1 This method 1s based on Chapman, H.D., "Cation-exchange Capacity,"pp. 891-900, In C.A. Black (ed.), Method of Soil Analysis, Part 2: Chemicaland Microbiological Properties, Am. Soc. Agron., Madison, Wisconsin (1965).


flR300829)

METHOD *O«i

CAPACITY or MILS (sooxu* ACETATE)

C7. 1

Oout aanpla.tranefer to

eentrifuga tub*

7.2

Add7.8eolutlon:

centrifuge:Decant w««ninginto flack

AddN«OAc •elutien;ccntrlfuga

7.3

Meant liquid:r«p««t 3 nor*tlnaa

7.4

7.7

prpcadur*K tlM«i

7.C OllutaeoaeinadwaaningMltn aaaoniunacatat*aolutlon

Add laoDropylaleonpl; anaka:cantrifuga

7.5

Hapeat C «orattawa

7.1

Oataralna•Pdlu«cpncantratlon

09081 - 4

Revision oDate September 1986

f lR300830




A. EPA Region/Client:EPA-REGION III-ARCS III


c. Telephone Number; (301) 266-9180





Analysis of 5 soil samples for Grain Size Distribution, Bulkdensity, and soil moisture by the methods listed in Item 7.


5 low concentration soil samples for the above analysis.

3. Purpose of analysis (specify whether Super fund (enforcement orremedial action), RCRA, NPDES, etc.):

RI/FS - ARCS III


AR30083I


To be determined.


To be determined.

Samples will be shipped overnight by overnight air carrier. Thisschedule is tentative and is dependant on the project remaining onschedule. Sampling may continue into the week of


Written results wir.r.in 35 days of the receipt of the last sample.

7. Analytical protocol required (attach copy if other thanprotocol currently used in this program):Grain size - Analysis by ASTM D-422-63 (Attachment 1) withrequired "Dry Preparation of Soil Samples..." ASTM D-421(Attachment 2) and Sieve Accuracy Testing, Chapter 3 from"Procedures in Sediment Petrology (Attachment 3) . balancecheck using NBS Class "S" weights.

Bulk density - Chapter 13 of Methods of Soil Analysis -Agronomy No. 9 (Attachment 4) .

Soil moisture - ASTM D2216-80 (Attachment 5).

All methods are attached.

8. Special technical instructions (if outside protocolrequirements, specify compound names, GAS numbers, detectionlimits, etc.):Grain Size - see Attachment 6.


See Attachment 7.


See Attachment 6.


Jeff Orient - NUS Corporation (412)-788-1080.



Grain size - must meet report requirements and data specificationsas stated in ASTM D-422-63, Section 18, page 93.


Audits Required . Frequency of Audits (Percent or Concentration)

Sieve calibration See Attachment 3 Table 1,. pages 49-50and 65-106

Balance calibration One per batch As per manufacturer'sspecifications (also

record in deliverables)


If sieves do not meet sieve accuracy requirements, new sievesthat meet the requirements must be used.


Gregory L. Zimmerman - NUS Corporation - (412) 788-1080.June 6, 1991.


Please return this request to the Sample Management Office as soonas possible to expedite processing of your request for SpecialAnalytical Services. Should you have any questions or need anyassistance/ please contact your local Regional representative atthe Sample Management Office.

HR3Q0833

Designation: D 422 - 63 (Reapprove<J 1972)<1

Standard Method forParticle-Size Analysis of Soils1

Thu standard is issued under the fued designation D 422: the number immediately followmi the designation indicates the -.ear ofanginal adoption or. in the cue of revision, the year of last revision. A number in parentheses indicates the year of last reapproval *superscript epsilon (<) indicates an editorial change unce the last revision or reapproval.

1 NOTE—Section : *is added editonally and subsequent sections renumbered in July I9M

1. Scop«I. I This method covers the quantitative determination of

the distnbution of panicle sizes in soils. The distribution ofpanicle sizes larger than 75 jam (retained on the No. 200sieve) is determined by sieving, while the distribution ofparticle sizes smaller than 75 um is determined by asedimentation process, using a hydrometer to secure thenecessary data (Notes 1 and 2).

NOTE I—Separation may be made on the No. 4 (4.75-mm). No. 40(423-tim), or No. 200 (75-um) sieve instead of the No. 10. For whateversieve used, the sue shall be indicated in the report.

NOTE 2—Two types of dispersion devices are provided: (/) ahith-spwd mechanical stirrer. and (2) air dispersion. Extensive invesa-jations indicate that air-dispersion devices produce a more positivedispersion of plastic soils below the 20-um size and appreciably lestdegradation on all sizes when used with sandy soils. Became of thedefinite advantages favoring air dispersion, its use is recommended. Theresults from the two types of devices differ in matnitude. dependingupon soil type, leading to marked differences m particle size distribu-tion, especially for sizes finer than 20 um.

2. Referenced Documents2.1 ASTM Standards:D 421 Practice for Dry Preparation of Soil Samples for

Particle-Size Analysis and Determination of SoilConstants2

E 11 Specification for Wire-Cloth Sieves for TestingPurposes3

E 100 Specification for ASTM Hydrometers4

3. Apparatus3.1 Balances—A balance sensitive to 0.01 f for weighing

the material passing a No. 10 (2.00-mm) sieve, and a balancesensitive to 0.1 % of the man of the sample to be weighed forweighing the material retained on a No. 10 sieve.

3.2 Stirring Apparatus—Ether apparatus A or B may beused.

3.2.1 Apparatus A shall consist of a mechanically oper-ated stirring device in which a suitably mounted electricmotor turns a vertical shaft at a speed of not less than 10 000rpm without load. The shaft shall be equipped with a

' This method is under the juradicaoa of ASTM Comaum* O>ll on Soil andRock and is the dim mponability of Subeemminw D 11.03 oo Texture.Ptattcny. and Density Ounctcraucs of Soils.

Current •dmon approved Nov. 21. 196* Origmaly pubfatad 1935. kepiacas0422-62.

: Annual Book of ASTM Siaitlanb, VoJ 04.011 Annul look of ASTM Stand**. Voi 14.02.4 Annual look of ASTM Slander*. Vol 14.01.

replaceable stirring paddle made of metal, plastic, orrubber, as shown in Fig. 1. The shaft shall be of such Itthat the stirring paddle will operate not less than "* in.mm) nor more than I1/: in. (38.1 mm) above the bottcthe dispersion cup. A special dispersion cup conformieither of the designs shown in Fig. 2 shall be provided tothe sample while it is being dispersed.

3.2.2 Apparatus B shall consist of an air-jet dispecup3 (Note 3) conforming to the general details shown n3 (Notes 4 and 5).

NOTE 3—The amount of air required by an air-jet dispersionof the order of 2 fWmin: some small air compressors are not cap*supplying sufficient air to operate a cup.

NOTE 4—Another air-type dispersion device, known as a ditptube, developed by Chu and Davidson at Iowa State College, ha:shown to give results equivalent to those secured by the air-jet dispcups. When it is used, soaking of the sample can be done isedimentation cylinder, thus eliminating the need for transfer™slurry. When the air-dispersion tube is used, it shall be so mdicathe report

NOTE i—Water may condense in air lines when not in usewater must be removed, either by using a water trap on the air line.blowing the water out of the line before using any of the adispersion purposes.

3.3 Hydrometer—An ASTM hydrometer, graduateread in either specific gravity of the suspension or gramlitre of suspension, and conforming to the requirementhydrometers 151H or 152H in Specifications E 100. Disions of both hydrometers are the same, the scale betnonly item of difference.

3.4 Sedimentation Cylinder—A glass cylinder essen18 in. (457 mm) in height and 2'/i in. (63.5 mm) in diarrand marked for a volume of 1000 mL. The inside diarshall be such that the 1000-mL mark is 36 ± 2 cm frorbottom on the inside.

3.5 Thermometer—A thermometer accurate to(0.3-0.

3.6 Sieves—A series of sieves, of square-mesh wovencloth, conforming to the requirements of SpecificationA full set of sieves includes the following (Note 6):

' DctttM «oitiag dnrnp fer tfefc cap an avatttttt at a nominal cotthe AnerkM Society fer Tonng sad Materials, 1916 Race St. Philadcipt19103. Order Adjwa N* 12-40422040.

87

0 422

-No. 18 8W <J4< 0.049*

Chrom* Plated

Punch0.203'

(a) (b)

00010,03

0,0491 24

0.203S.18 190

FM3. 1 0«t»tf o< Stirring PaddtM

3-m. (75-mml No. lOC.OO-mm):-in. (50-mm) No. :0 (850-um)I'TiB. 1375-mm) No. 40 (423-um>1-iB. Ui.O-mm) No. 60 (2JO-)im>»,-.n. (I90-mm) NO. 140 (106-um)'Vm. (9.5-mm> No. :00 (75^m)No. 4(4.75-mm) •

NOTE 6—A set of sieves giving uniform spacing of points for thegraph, as required in Section 17, may be used if desired. This wt consistsof the following sieves:

3-m. (75-mm)ivj-m. (J7.5.mm)"wn. (190-mm)'Vm. (9.5-mm)No. *(4,75-mm)No. 8 (2.36-mm)

No. l6(l . lS-mm>No. 30 (600-tuntNo. 50 (300-wm)No. 100(l50-um)No. !00 (75-um>

3.7 Water Bath or Constant-Temperature Room—Awater bath or constant-temperature room for maintainingthe soil suspension at a constant temperature during thehydrometer analysis. A satisfactory water tank is an insulatedtank that maintains the temperature of the suspension at aconvenient constant temperature at or near 68*F (20*Q.Such a device is illustrated in Fig. 4. In cases where the workis performed in a room at an automatically controlledconstant temperature, the water bath is not necessary.

3.8 Beaker—A beaker of 250-rnL capacity.3.9 Timing Device—*, watch or clock with a second

hand.

4. Dispersing Agent4.1 A solution of sodium bexametapoosphate (sometimes

called sodium metaphosphate) snail be used in distilled ordemineralued water, at the rate of 40 g of sodiumhexametaphosphate/litre of solution (Note 7).

Sort 7—Solutions of this salt, if acidic, slowty revcn or aydroiyaback to the onnophosphau form with a resultant decnM in dispeniwaction. Solutions should bt prepared frequently (at lean one* « month)or adjusted to pH of I or 9 by meu* of sodium carbonate; Boctiatc ininf solutions should have tb* daft of preparation marked oa

4.2 All 'water used shall be either distilled orlemineralized water. The water for a hydrometer test snail

•175'diam.-

Baffle \Location *H

Plan

ZS'ttom.——|

1.333

2.8M

37S99.2

no. a

be brought to the temperature that is expected to prevailduring the hydrometer test For example, if the sedimenta-tion cylinder is to be placed in the water bath, the distilled ordemineralized water to be used shall be brought to thetemperature of the controlled water bath; or, if the sedimen-tation cylinder is used in a room with controlled tempera-ture, the water for the test shall be at the temperature of theroom. The bask temperature for the hydrometer test is 68*F(20*Q. Small variations of temperature do not introducedifferences that are of practical significance and do notprevent the use of corrections derived as prescribed.

5.

ou:du:ccr516'thepurSUt"foi l

shathe

5be;g t c

5

wasretapencak

V.

PUNPanand

6Tirr

f lR300835

<SD» 0422

CSOSS SECTIONCo» 9.

RO. 3 Air-J*t Oispcraton Cup* of Apparatus •

prevailnenta-lledorto thetimen-npera-of ties68T•odulo no*

5. Test Sample5.1 Prepare the test sample for mechanical analysis as

outlined in Practice D421. During the preparation proce-dure the sample is divided into two portions. One portioncontains only particles retained on the No. 10 (2.00-mm)sieve while the other portion contains only particles passingthe No. 10 sieve. The mass of air-dried soil selected forpurpose of tests, as prescribed in Practice D421, shall besufficient to yield quantities for mechanical analysis asfollows:

5.1.1 The size of the portion retained on the No. 10 sieveshall depend on the maximum size of particle, according tothe following schedule:

Nominal Diameter ofUrjen Pamela.

in. (mm)V, (9.5)V. (19,0)

1 (25.4)I1/: (38.1)2 (JO.S)3 (76.2)

Approximatt MinimumMatt of Portion. (

50010002000300040005000

5.1.2 The size of the portion pasting the No.. 10 sieve shallbe approximately 115 g for sandy soils and approximately 65g for silt and clay soils.

5.2 Provision is nude in Section 5 of Practice D42I forweighing of the air-dry soil selected for purpose of tests, theseparation of the soil on the No. 10 sieve by dry-sieving andwashing, and the weighing of the washed and dried fractionretained on the Na 10 sieve. From these two masses thepercentages retained and passing the No. 10 sieve can becalculated in accordance with 12.1.

NOTI 8—A check on the mas* values and the tborouabaeM ofpulverization of the dads may be Mcured by weifhiat the porno*pastas the No. lOsroi^idaddi!* this vaJue to the matt of the washedud ovetHimd portico retained on the No. 10 yew.

SIEVE ANALYSIS OF POUTON RETAINED ON NO. ItCLOt-M) SIEVE

6. Procedure6.1 Separate the portion retained on the No. 10 (2.00-

mm) sieve into a series of fractions using the 3-in. (75-mra).

22-21

29.43

78.2814151.2

143M

TO. 4 Irnmeaad Water Sam

2-in. (50-mm), IVi-in. (37.5-mm), 1-in. (25.0-mm), '(19.0-mm), ft-in. (9.5-mmX No. 4 (4.75-mm), and Ncsieves, or as many as may be needed depending onsample, or upon the specifications for the material utest

6.2 Conduct the sieving operation by means of a laand vertical motion of the sieve, accompanied by a jiaction in order to keep the sample moving continuouslythe surface of the sieve. In no case turn or maniptfragments in the sample through the sieve by hand. Contsieving until not more than 1 mass % of the residuesieve passes that sieve during 1 min of sieving. Vmechanical sieving is used, test the thoroughness of sieby using the hand method of sieving as described above

6.3 Determine the mass of each fraction on a balconforming to the requirements of 3.1. At the enweighing, the sum of the masses retained on all the sused should equal dosery the original mass of the quasieved.

89S R 3 0 0 8 3 6 -

HYDROMETER «i>0 SIEVE \N\LYSIS OF PORTIONPASSING THE NO. 10 (2.00-mm> SIEVE

7. Determination of Composite Correction for HydrometerReading

7.1 Equations for percentages of soil remaining in suspen-sion, as given in 14.3. are based on the use of distilled ordemineralized water. A dispersing agent is used in the water,however, and the specific gravity of the resulting liquid isappreciably greater than that of distilled or demineralizedwater.

7 . 1 . 1 Both soil hydrometers are calibrated at 68"F (20'C),and variations in temperature from this standard tempera-ture produce inaccuracies in the actual hydrometer readings.The amount of the inaccuracy increases as the variationfrom the standard temperature increases.

7.1.2 Hydrometers are graduated by the manufacturer tobe read at the bottom of the meniscus formed by the liquidon the stem. Since it is not possible to secure readings of soilsuspensions at the bottom of the meniscus, readings must betaken at the top and a correction applied.

7.1.3 The net amount of the corrections for the threeitems enumerated is designated as the composite correction,and may be determined experimentally.

7.2 For convenience, a graph or table of compositecorrections for a series of 1* temperature differences for therange of expected test temperatures may be prepared andused as needed. Measurement of the composite correctionsmay be made at two temperatures spanning the range ofexpected test temperatures, and corrections for the interme-diate temperatures calculated assuming a straight-line rela-ionship between the two observed values.

7.3 Prepare 1000 mL of liquid composed of distilled ordemineralized water and dispersing agent in the sameproportion as will prevail in the sedimentation (hydrometer)test. Place the liquid in a sedimentation cyclinder and thecylinder in the constant-temperature water bath, set for oneof the two temperatures to be used. When the temperature ofthe liquid becomes constant, insert the hydrometer, and,after a short interval to permit the hydrometer to come to thetemperature of the liquid, read the hydrometer at the top ofthe meniscus formed on the stem. For hydrometer 151H thecomposite correction is the difference between this readingand one; for hydrometer 15 2H it is the difference betweenthe reading and zero. Bring the liquid and the hydrometer tothe other temperature to be used, and secure the compositecorrection as before.

8. Hygroscopic Motsttar*3.1 When the sample is weighed for the hydrometer test,

weigh out an auxiliary portion of from 10 to 15 g in a smallmetal or glass container, dry the sample to a constant mast inan oven at 230 * 9T (110 ± S'Q, and weigh again. Recordthe masses.

9. Dispersk* of Soil Sample9.1 When the soil is mostly of the clay and silt sizes, weighit a sample of air-dry soil of approximately 20 g. When the

soil is mostly sand the sample should be approximately 100g.

9.2 Place the sample in the 250-mL beaker and co^er --nth125 mL of sodium hexametaphosphate solution (40 g/L;Stir until the soil is thoroughly wetted. Allow to soak for atleast 16 h. .

9.3 At the end of the soaking period, disperse the samplefurther, using either stirring apparatus A or B. [f stirringapparatus A is used, transfer the soil - water slurry from thebeaker into the special dispersion cup shown in Fig. 2.washing any residue from the beaker into the cup withdistilled or demineralized water (Note 9). Add distilled ordemineralized water, if necessary, so that the cup is morethan half full. Stir for a penod of I mm.

More 9—A large size syringe is a convenient device for handling thewater in the washing operation. Other devices include the *ash-*aterboule and a hose with nozzle connected to a pressurized distilled watertank.

9.4 If stirring apparatus B (Fig. 3) is used, remove thecover cap and connect the cup to a compressed air supply bymeans of a rubber hose. A air gage must be on the linebetween the cup and the control valve. Open the controlvalve so that the gage indicates 1 psi (7 kPa) pressure (Note10). Transfer the soil - water slurry from the beaker to theair-jet dispersion cup by washing with distilled ordemineralized water. Add distilled or demineralized water, ifnecessary, so that the total volume in the cup is 220 mL, butno more.

NOTE 10—The initial air pressure of 1 psi is required to prevent thesoil • water mixture from enterint the air-jet chamber when the rautureis transferred to the dispersion cup.

9.2 Place the cover cap on the cup and open the aircontrol valve until the gage pressure is 20 psi (140 kPa).Disperse the soil according to the following schedule:

Plasticity IndexUnder 56 to 20Over 20

Dispersion Penod.mm

51013

Soils containing large percentages of mica need be dispersedfor only 1 min. After the dispersion period, reduce the gagepressure to I psi preparatory to transfer of soil - water slurryto the sedimentation cylinder.

10. HydroaMter Teat10.1 Immediately after dispersion, transfer the soil • water

slurry to the glass sedimentation cylinder, and add distilledor demineralized water until the total volume is 1000 mL.

10.2 Using the palm of the hand over the open end of thecylinder (or a rubber stopper in the open end), turn thecylinder upside down and back for a period of I min tocomplete the agitation of the slurry (Note 11). At the end of1 min set the cylinder in a convenient location and takehydrometer readings at the following intervals of time(measured from the beginning of sedimentation), or as manyas may be needed, depending on the sample or the specifica-tion for the material under test 2. 2. 15, 30, 60, 220, and1440 min. If the controlled water bath is used, the sedimen-tation cylinder should be placed in the bath between the 2-and 2-min readings.

Son II—Tht nume«r of turn during this minute should I*approximately 60. counting Uit tura upodt down and back as two turn*

90

'^tH 300 83 7

0422

g/Ufo-

amplelining•m therig. 2,

led ormore

l ing theh-waterd water

ve theiply byic line:ontrol(Noteto the

ed orater, ifiL, but

v«ntthcmixtun

the) ki ..

>persedhe gager slurry

- waterlistilled) mL.1 of theirn themin toend of

id takeif times manyccifica-50, anddimen-i the"

ould btvoturna.

'! remaining in the bonom of the cylinder dunng the first fewshould be loosened by vigorous shaking of the cylinder while it is

„ the inverted position.10.3 When it is desired to take a hydrometer reading.

carefully insert the hydrometer about 20 to 25 s before thefading is due to approximately the depth it will have whenthe reading is taken. As soon as the reading is taken, carefullyremove the hydrometer and place it with a spinning motionin a graduate of clean distilled or demineralized water.

N'OTE 12 — It is important to remove the hydrometer immediatelyi/ter each reading. Readings shall be taken at the top of the meniscusformed by the suspension around the stem, since it is not possible to

readings at the bonom of the meniscus.10.4 After each reading, take the temperature of the

suspension by inserting the thermometer into the suspen-sion.

11. Sieve Analysis11.1 After taking the final hydrometer reading, transfer

the suspension to a No. 200 (75-um) sieve and wash with tapwater until the wash water is clear. Transfer the material onthe No. 200 sieve to a suitable container, dry in an oven at230 ± 9*F (1 10 ± 5*Q and make a sieve analysis of theportion retained, using as many sieves as desired, or requiredfor the material, or upon the specification of the materialunder test.

CALCULATIONS AND REPORT

12. Sieve Analysis Values for the Portion Coarser thai tbtNo. 10 (2.00-mm) Sieve

12.1 Calculate the percentage passing the No. 10 sieve bydividing the mass passing the No. 10 sieve by the mass of soUoriginally split on the No. 10 sieve, and multiplying the resultby 100. To obtain the mass passing the No. 10 sieve, subtractthe mass retained on the No. 10 sieve from the original mass.

12.2 To secure the total mass of soil passing the No. 4(4.75-mm) sieve, add to the mass of the material passing theNo. 10 sieve the mass of the fraction passing the No. 4 sieveand retained on the No. 10 sieve. To secure the total mass ofsoil passing the ]Vin. (9.5-ram) sieve, add to the total mast ofsoil passing the No. 4 sieve, the mass of the fraction passingthe 34-in. sieve and retained on the No. 4 sieve. For theremaining sieves, continue the calculations in the samemanner.

12.3 To determine the total percentage pasting for eachsieve, divide the total mas* passing (see 12.2) by the totalmass of sample and multiply the result by 100.

13. Hygroscopic Mofcfcn Comedos Factor13.1 The hydroscopk moisture correction factor is the

ratio between the mass of the oven-dried sample and theair-dry mass before drying. It is a number less than one,except when there is no hygroscopic moisture.

14. PerctatagM at Soil !•14.1 Calculate the oven-dry mass of soil used in the

hydrometer analysis by multiplying the air-dry man by thehygroscopic moisture correction factor.

TASLf 1 VafuMofCoiGravttt

Spaofc Ortvtty2.992.902852.802.752.702.S52.602.552502.4S

* For uw «i aquation for pareHydrofflatar 152H.

T«eoc« Ft«or. a. for Wffar»m Sf«• of Soil PirtJcl4a-»

Conctjcn F»ctor*09409509«0,9709f0991001 011 021.031 05

•ntaga of so* rtmamg «i suioanaon *r

14.2 Calculate the mass of a total sample representhe mass of soil used in the hydrometer test, by divid:oven-dry mass used by the percentage passing the '(2.00-mm) sieve, and multiplying the result by 10Cvalue is the weight W in the equation for percremaining in suspension.

14.3 The percentage of soil remaining in suspensionlevel at which the hydrometer is measuring the densitysuspension may be calculated as follows (Note 13hydrometer 151H:

P- KIOOOOO/W) x GKG - G,)K* - G,)NOTi 13—The bracketed portion of the equation for hydi

1 j 1H is constant for a serkt of readings and may be calculated fthen muloptiad by the portion in the parentheses.For hydrometer 152H:

P - (Ra/tT) x 100where:a » correction faction to be applied to the read

hydrometer 152H. (Values shown on the seacomputed using a specific gravity of 2.65. Confactors are given in Table 1),

P » percentage of soil remaining in suspension at that whkb the hydrometer measures the densitysuspension,

R » hydrometer reading with composite correcticplied (Section 7),

W m oven-dry mass of soil in a total test samplesented by mas* of soil dispersed (see 14.2), g,

G • specific gravity of the soil particles, andG, • specific gravity of the liquid in which soil partic

suspended. Use numerical value of one ininstances in the equation. In the first instantpossible variation produces no significant efTecin the second instance, the composite correction-is based on a value of one for </,.

15. DiaanwofSotlPaitklec15.1 The diameter of a particle corresponding

percentage indicated by a given hydrometer reading sicalculated accordint to Stokes* law (Note 14), on UKthat a particle of this diameter was at the surfacesuspension at the beaiaatntof sedimentation and hadto the level at which the hvdrometeris measuring the cof the suspension. Accordint to Stokes' law;

D - V{30«/9iO«? - <?,)] x L/T

91

where:D *

(7G,

diameter of particle, mm,coefficient of viscosity of the suspending medium (inthis case water) ia poises (varies with changes intemperature of the suspending medium),distance from the surface of the suspension to thelevel at which the density of the suspension is beingmeasured, cm. (For a given hydrometer and sedimen-tation cylinder, values vary according to the hydrom-eter readings. This distance is known as effectivedepth (Table 2)),interval of time from beginning of sedimentation tothe taking of the reading, mio.specific gravity of soil particles, andspecific gravity (relative density) of suspending me-dium (value may be used as 1.000 for all practicalpurposes).

MOTE 14 — Since Stokes' law considers the terminal velocity of asingle sphere failing in an infinity of liquid, the sizes calculated representthe diameter of spheres that would fall a the same rate as the soilpanicles.

15.2 For convenience in calculations the above equationmay be written as follows:

where:K • constant depending on the temperature of the suspen-

sion and the specific gravity of the soil particles. Valuesof K for a range of temperatures and specific gravitiesare given in Table 3. The value of AT does not change fora series of readings constituting a test, while values of Land r do vary.

15.3 Values of D may be computed with sufficient accu-racy, using an ordinary 10-in. slide rule.

NOTE I 5— The value of £ is divided by T using in* A- and 3-scales.the square root being indicated on the O-icalc. Without ascertaining ttatvalue of the square root it may be multiplied by K. using either the C- orC/.scale.

16. Sievt Analysis Value* for PortkM Finer than No. 10(2.00-ouB) Sk?e

16.1 Calculation of percentages passing the various sievesused in sieving the portion of the sample from the hydrom-eter test involves several step*, The first step is to calculatethe mass of the fraction that would have been retained on theNo. 10 sieve had it not bee* removed. This mass is equal tothe total percentage retained am the No. 10 sieve (100 minustotal percentage ptsnDf) times the mass of the total samplerepresented by the mast of soil used (as calculated in 14.2Xand the result divided by 100.

16.2 Calculate next the total mass passing the No. 200sieve. Add together the fractional masses retained on all thesieves, including the No. 10 sieve, and subtract this sum fromthe mass of the total sample (as calculated in 14.2).

16.3 Calculate next the total masses passing each of theMher sieves, in a manner similar to that given in 12.1

16.4 Calculate last the total percentages passing by di-viding the total mass passing (as calculated in 16.3) by thetotal mass of sample (as calculated in 14.2X and multiply the-result by 100.

0422

TABU 2 V«h*9 of &ff*ct*v« Otptt 8«M<f on KYdrom«t.x andaNhinniirtnn Cyfcwfrr of Sp«crt«d 3iz«r*

H-

,

^

HyOromvUT l5tH

ActUM EffKtM'OfOHWtBr OcpttitRMdinf I. cm

1 000 18.31001 180t 002 15.81.003 15.51 004 15.21 008 15.0

1 008 14.71007 1441 008 142t 009 13.91010 13.7

1011 13.41 012 13.11 013 12.91014 12.81 019 12.3

1018 12.11.017 1151.018 11 51019 1131.020 11.0

1.021 10.71.022 10.51023 10.2.1.024 10.01.028 9.7

1028 9.41.027 9.21028 3.91029 8.81.030 8.4

1031 8.11.032 781.033 781.034 7.31038 701.038 8.81.037 8.51.031 8.2

* V*JM Of tflMM C*P») 1

L-•rat

Hyoi•omtwr 152HActu« srrtaiv* A«U«

Hyofomwr O^xn. HyopormwrflMdirq

012345

373910

1112131415

1817181920

2122232423

2827282930

L. cm18.318.113.015313.8155

15.315.2150148147

145143142140138

13.713.513.313.213.0

12.912.712.512.412.2

12.011.911.711511 4

z»»an)3132333433

3837333940

41

42434445

4847444950

515253 .S455

5857585960

Eff»CTJV«0*Offl,I. an11 2tl 110910.7108

'0410210.1399 7

98 {9492 i9.139

383.83.43.38.1

7973787473

7 17033388.5

*9 dRUMM frOfll ttW fUrttton1

t, «-t*m -WM

L — •flMlvv o^apsltt cm,L« • dattkWi) oflij thai staVn of th»> hyoftyntisy front tfw top of ttw bust) ID tf*

n rti tof • ftydrQOTsMaV rMdbiQi cnt.Cf"•/*v«FattV*AgtjMPfl

t,

* 0¥«VH aWQan Qf tns) HyOJUflaMaV OUB* CM»• vofem of hycwww bun. cm*, md• O)M*4Ktlem WH Of M

UMuMtfnafeuMingmvr Mn nyttomm. 1S1M OT• 14.0cm-87.0 em*• 27 8 em*

. IH« «HI ^ 1CtU*nyomnwr lainc• lOJemtarirMdhaot

^^_^^Hl ^yHmvraiH•MMTHrtiS2Mr

1000

tcytoc*»2m

r. cm*MtotOWK

r

24 em for • rsadhi of t.om1S2H

• 2.3 cm tar • rMdne of SO oMra

17. Crag*17.1 When the hydrometer analysis performed, a grapft

92f lR300839

D 422

>r and

••ectrvw'•Otn... cm11 211 1109'07•06

10410210 1999,7

9.694929,189

8.8888.48,38.1

7978767473

71706,8686.5

wtr»

TABU 3 VahM* of K for UM In Equation for Computing Dwmc*rmparatur*.

•c1817181920

2122232425

2627282930

_ _j n«^ai J A t« '-*- .Aw or riniciv in nyorofntttf A/ttityftJtSoaofle OravMy of Sol Pvooaa

2.450.015100.015110.014920.014740.01454

0014340014210014040013840.01372

0.013570013420,013270,013120.01294

2.500.015050.014460014470.014490.01431

0014140.013970013410013650.01349

0.013340,013190.013040.012900,01276

2550014410,014420014430.014250.01404

0.013910013740.013540,01342001327

0,013120.012970.012830012690.01254

2.600014570,014390014210,014030.01344

0.013490.013530,013370.013210,01304

0.012910.012770012640,012490.01239

2850.014350,014170,013990,013420,01344

0.013440,013320.013170.013010.01294

0.012720.012540.012440.012300.01217

2.700.014140.013940.013790.013410.01344

0.013240.013120.012970.012820.01247

0012530.012390,012590.012120.01199

2.750,013940,013740013540.013420,01329

0.013090.012940.012790.012640.01249

0.012350,012210.012040.011940.01182

2,800013740.013540.013390.13230.01307

0.012910.012780.012610.012440.01232

0.012180012040.011910,011780.01185

20010010010,010,01

0010010,01001001

001001001001001

of the test results shall be made, plotting the diameters of theparticles on a logarithmic scale as the abscissa and thepercentages smaller than the corresponding diameters to anarithmetic scale as the ordinate. When the hydrometeranalysis is not made on a portion of the soil, the preparationof the graph is optional, since values may be secured directlyfrom tabulated data.18. Report

18.1 The report shall include the following:18.1.1 Maximum size of particles,18.1.2 Percentage passing (or retained on) each sieve,

which may be tabulated or presented by plotting on a graph(Note 16),

18.1.3 Description of sand and gravel particles:18.1.3.1 Shape—rounded or angular,18.1.3.2 Hardness—hard and durable, soft, or weathered

and friable,18.1.4 Specific gravity, if unusually high or low,18.1.5 Any difficulty in dispersing the fraction passing the

So. 10 (2.00-mm) sieve, indicating any change in type andamount of dispersing agent, and

18.1.6 The dispersion device used and the length of thedispersion period.

Non 16—Tbis tabulation of ptpa iqnauiu tb* gradation of thtsample tated. If paroda latter thin tfaoaa cmitainari in the auapte w«rtremoved before taunt, tht report shall so *a* ftviaj the amount andmaximum "**

18.2 For material* toted for compliance with definitespecifications, the ftirioas called for in such specificationsshall be reported. Tteftictions smaller than the No. 10 sieveshall be read from toe graph.

18.3 For materials for which compliance with definitespecifications is not indicated and when the soil is composed

almost entirely of particles passing the No. 4 (4.7!sieve, the results read from the graph may be reporfollows:(/)(2)

Gnv»».Sand.(a) Coane

No. 10(») Madiua

3-w. tad rciauMd oa No. 4No. 4 neve tad retaiMd OB N<

No. 4 wvt tad

•••.<JO

ad. tri No. 10 MVC tod rewaad oa

(3)(4)

N0.40MN*(c) Fun «ad,

200 amSift am 0.074 to 0.005 maday na. flaaflar thta 0.005 ma

CoUotd*. «THhf that 0.001 ma

No, 40 mm tad mtiort oa No.

18.4 For materials for which compliance with d<specifications is not indicated and when the soil comaterial retained on the No. 4 sieve sufficient to reqsieve analysis on that portion, the results may be reporfollows (Note 17):

SIEVE ANALYSIS

SiavaSiaaPercent

PUBZ

Wm.2-ia.IVwa.i-ia.

Na 4 (4.7jNalO(ZONo, 40 (425-n»)

HYDROMETBX ANALYSIS0.074 urn0.005 aw0.001 aa

Non 17—No. I (2J6HUB) and Na 50 (300^tn>)juaamad far Na 10 and Na 40 aim

7n0 Ayianoaff sootly fOf ratttt afvw4ft an/ Mfiy /nanitaMtf At tftfi landvA UaM o^tftit atvuaftf anapaanr ng«a, antf Mt ralr * MMnamar* at aucft npna, ara tn**t tf*r

a graph-

THt atVMM * auo/aor »/wafcw at any am 6y 9m rBXSTM(I you /nay

your oammana wf me**ffyouM mar your

MT9Tflt>

ana* /ffuat a> fawwvatf avavy jaw )^a/v antf

at a nweaWf rf nt faaponad*a at Manrv )w *wu« m*a yor

f l R 3 0 D 8 l * 0

Designation: D 421 - 85

Standard Practice forDry Preparation of Soil Samples for Particle-Size Analysis andDetermination of Soil Constants1

This standard is issued under the fixed designation 042!'. the number immediately following the designation indicates the year ofanginal adoption or. in the case of revision, the year of list revision. A number in parentheses indicates the year of last reapproval. *isuperscript spsilon.u) indicates an editorial change since the last revision or reapproval.

1. Scope1.1 This practice covers the dry preparation of soil sam-

ples as received from the field for panicle-size analysis andthe determination of the soil constants.

1.2 This standard may involve hazardous materials, oper-ations, and equipment. This standard does not purport toaddress all of the safety problems associated with its use. It isme responsibility of whoever uses this standard to consult andestablish appropriate safety and health practices and deter-mine the applicability of regulatory limitations prior to use.

2. Referenced Documents2.1 ASTM Standards:D 2217 Practice for Wet Preparation of Soil Samples for

Particle-Size Analysis and Determination of SoilConstants2

E 11 Specification for Wire-Cloth Sieves for TestingPurposes3

3. Significance and Use3.1 This practice can be used to prepare samples for

particle-size and plasticity tests where it is desired to deter-mine test values on air-dried samples, or where it is knownthat air drying does not have an effect on test results relativeto samples prepared in accordance with Practice D 2217.

4. Apparatus4.1 Balance, sensitive to 0.1 g.4.2 Mortar and Rubber-Covered Pestle, suitable for

breaking up the aggregations of soil panicles.4.3 Sieves—A series of sieves, of square mesh woven wire

cloth, conforming to Specification E l l . The sieves requiredare as follows:

No. 4(4.75-mm)No. 10 (2.00-mm)No. 40 (425-um)

4.4 Sampler—A. rifflequartering the samples.

sampler or sample splitter, for

air at room temperature until dried thoroughly. Break up theaggregations thoroughly in the mortar with a rubber-coveredpestle. Select a representative sample of the amount requiredto perform the desired tests by the method of quartering orby the use of a sampler. The amounts of material required toperform the individual tests are as follows:

5.1.1 Panicle-Size Analysis—For the panicle-size anal-ysis, material passing a No. 10 (2.00-mm) sieve is required inamounts equal to 115 g of sandy soils and 65 g of either sator clay soils.

5.1.2 Tests for Soil Constants—For the tests for soilconstants, material passing the No. 40 (425-um) sieve isrequired in total amount of 220 g, allocated as follows:

Test GramsLiquid limitPlastic limnCentrifuge moisture equivalentVolumetric shrinkageCheck tests

10015103065

5. Sampling5.1 Expose the soil sample as received from the field to the

6. Preparation of Test Sample6.1 Select that portion of the air-dried sample selected for

purpose of tests and record the mass as the mass of the totaltest sample uncorrected for hygroscopic moisture. Separatethe test sample by sieving with a No. 10 (2.00-mm) sieve.Grind that fraction, retained on the No. 10 sieve in a mortarwith a rubber-covered pestle until the aggregations of soilpanicles are broken up into the separate grains. Thenseparate the ground soil into two fractions by sieving with aNo. 10 sieve.

6.2 Wash that fraction retained after the second sievingfree of all fine material, dry, and weigh. Record this mass asthe mass of coarse material. Sieve the coarse material, afterbeing washed and dried, on the No. 4 (4.75-mm) sieve andrecord the mass retained on the No. 4 sieve.

7. Test Sample for Particle-Size Analysis7.1 Thoroughly mix together the fractions passing the No.

10 (2.00-mm) sieve in both sieving operations, and by themethod of quartering or the use of a sampler, select a portionweighing approximately 115 g for sandy soils and approxi-mately 65 g for silt and clay soil for panicle-size analysis.

1 This practice is under the jurisdiction of ASTM Committee D-18 on Soil andRock and is the direct responsibility of Subcommittee D18.03 on Texture.Plasticity, and Density Chtnctensucs of Soils.

Current edition approved July 26. 1985. Published September 1985. Onpnillypublished as D 421 - 35 T. Last previous edition D 421 - 58 (1978)"

Annual Book of ASTM Standard}. Vol 04 083 Annual Book of ASTM Standards. Vol 14 02

8. Test Sample for Soil Constants8.1 Separate the remaining portion of the material passing

the No. 10 (2.00-mm) sieve into two parts by means of a No.40 (425-um) sieve. Discard the fraction retained on the No.40 sieve. Use the fraction passing the No. 40 sieve for thedetermination of the soil constants.

84

f l ' R 3 0 0 8 U l

0421

Tht Amman So&tty lor Tttting ind Mtttrttla ,'•*•« no position rtsotcting irm vttiaity at any oattnr right* tutnta <with try <ftm mtnttorma in m/» stvrttrt Uitrs of mi» stwatra in nontaty •Ovu*3 «* /Mtrminttnn of tn« »ti«3rtv ol any sucnp««nr f»a«», »ath»nt*of irttnngtirmfn of sucn ngna,

This jf«MWd.a Juty«ct fo rmsion * viy t/m« by m« rtsoonibb Itchmctl comrnfffM and must M rtviiwtd every Av« /MTS artY n« /•gvuttf. HOmrrMeofovta or witMrnrn. your comments at inviita vtfur lor rtvumn (rf tha stinava or lor taaitioril sttrxiirasand sfiouKI M norm**] to ASTU HMdguarttn. Your commtnts will rtctivt ctnful corwatrtiion st a matting of tht rnooraioit:scnmcti corrmttt*. wfucn you may antno. it you If* Ihn your comments nave not rtemvta a fur rtftrinq you snouid ma)tt yourstgws Known to tr* ASTM Commrtff on Stinatrat, I9JS flact Sf., Philtattpriit, PA T9703.

3

PROCEDURESIN SEDIMENTARY

PETROLOGY

Edited by

ROBERT E. CARVER

University of GeorgiaAthens, Georgia

ENVIRONMENTAL PROTECTION AGENCYANNAPOUS FIELD CrriCE

ANNAPOLIS SCIENCE CENTERANNAPOUS, MARYLAND 2U01

WILEY-INTERSCIENCE

A Division of John Wiley & Sons, Inc.New York • London • Sydney • Toronto

CHAPTER 3

SIEVE ANALYSIS

ROY L. INGRAM

University of North Carolina, Chapel Hill, North Carolina

The distribution of sizes of sedimentary particles with intermediatediameters in the range of 1/16 to 16 mm (sand and fine gravel) ismost commonly determined by sieving. In the United States, theUnited States Standard sieves or the Tyler Standard sieves (Table 1)are used by most workers.

TABLE 1 Sieve openings

WentworthScale,mm

16

8

Phi Scale

-4.00-3.75-3.50-3.25-3.00-2.75-2.50-2.25

V^Scale,mm

16.00013.45411.3149.5148.0006.7275.6574.757

U. S. Standard a

Opening,mm

16.013.511.29.518.006.735.664.76

Mesh.

Stt4

PerrnissableVariation

Average± %

33333333

Maxi.+ %

666666

1010

Tyler Mesh

2V,33V44

49

TABLE 1 Sieve openings (Continued)

:, ••;:•: %t;;*j£.3••s»V5»£'^.-±-3

• ^.i

•*fX--

fc»* •fell., si.^^K-» mvI '?™' ' .' "~-..-:-'•

A.S.T.M.. 1966, pp. 447-448.1 W. S. Tylcr Co.. 1967, p. 10.

.£-41'

WemworthScale,mm

4

2

1

.

1/2

1/4

1/8

1/16

1/32

Phi Scale

-2.00-1.75-1.50-1.25-1.00-0.75-0.50-0.25

0.000.250.500.751.001.251.501.752.002.252.502.753.003.253.503.754.004.254.504.755.00

V? Scale,mm

4.0003.3642.8282.3782.0001.6821.4141.1891.0000.8410.7070.5950.5000.4200.3540.2970.2500.2100.1770.1490.1250.1050.0880.0740.0620.0530.0440.0370.031

U.S. Standard"

Opening,mm

4.003.362.832.382.001.681.411.191.00

0.8410.7070.5950.5000.4200.3540.2970.2500.2100.1770.1490.1250.1050.0880.0740.0630.0530.0440.037

Mesh

5678

101214161820253035404550607080

100120140170200230270325400

PermissableVariation

Average± %

3333333355555555556666677777

Maxi.+ %

1010101010101010

15151515152525252525

I

Tyler b

Mesh ';

567

• 89

10121416202428 '3235 '42 •486065

40 80' 40

4040406060606060

100 '115150 '170200250270325400

50

' f lR3008l*5

(Continued)

U.S. Standard0

, >

0638)0>8U19304107950020.54!97250210177149125105088074062,053.04^.03-

lesh .J

567|8

10121416

' 1820253035404550607080

10012014017020C23C27C

I 32!r 40<

PermissibleVariation

Average±%

333333335555555555666667

) 7) 7j 7D 7

^laxi.•>-%

10101010101010101515151515252525252540404040406060606060

ryUr b \Mesh [

!5 i6 !7 '8 1

i9 '

10 .12 ',1416 ',2024 128 i32 '35424860 I6580

100115.150170200250270325400

!

I

i

PRELIMINARY TREATMENT 51

Before a sediment is sieved, the individual particles must beseparated from one another. Clay, cementing agents, and soluble saltsmust be removed. Sediments containing cementing agents thatcannot be removed without altering the individual particles cannotbe analyzed by sieving (e.g., most silica-cemented sandstone or mostcarbonate-cemented clastic limestones).

For sieve analysis, most sediments can be placed in one of threecategories: (A) sediment contains clay and cementing agents, (B)sediment contains clay, but does not need to be freed of cementingagents or pigments, and (C) sediment contains no clay, cementingagents, or soluble salts. All the steps in the procedure below shouldbe done for Type A sediments. Only those steps marked with a Dneed be done for Type B sediments. Only those steps marked with aA need be done for Type C sediments.

As the purposes and requirements of sieve analysis and the natureof sediments are variable, however, all of the steps should beconsidered and decisions made on each sample or suite of samples asto which steps will be performed or eliminated.

PRELIMINARY TREATMENT

D A 1. Dry sediment in air or in a 40°C oven.At higher temperatures any clay present may be baked into a

bricklike substance, thus making dispersal of the clay difficult.Temperature-sensitive minerals such as halloysite will also be alteredat higher temperatures.

D A 2. Break all clumps. Mash with fingers; use wooden or rubberpestle in a mortar; or use a wooden rolling pin. Use enough force toseparate the grains, but avoid breaking individual grains.

D A 3. Mix sediment thoroughly and split to get the desiredweight of sample. The exact size of sample that should be useddepends on several factors: the size and sorting of the sediment, theshape and roundness of the grains, the number of screens that will beused, the shaking time. Consequently exact weights cannot bespecified. As a preliminary guide the following approximate weightsare suggested: fine gravel—500 gm; coarse sand—200 gm; medium

52 SIEVE ANALYSIS

sand—100 gm; fine sand—25 to 50 gin. About 15 gm (range of 5 to25 gm) of material finer than 1/16 mm is needed if a pipette orhydrometer analysis is to be made. Another split may be necessarvfor the analysis of this fine material. Any of several alternateprocedures may be used.

Coning and QuarteringPour the sample on a flat surface so as to form a cone (Fig. 1). Use

a straight edge and separate the cone into four quarters. Push asidetwo of the alternate quarters. Mix the remaining two quarters andform another cone. Continue the quartering process until the desiredsize sample is obtained. Do not attempt to get a sample of an exactsize. For example, if a 100 gm sample is wanted, a sample within therange of 75 to 125 gm will usually be acceptable.

Fig. 1 Splitting sample by coning and quartering. (After W. S. Tyler Co., 1967,p. 13)

f t R 3 0 0 8 l 4 7

VLYSIS

5m. About 15 gm (range of 5 to6 mm is needed if a pipette orAnother split may be necessary

.erial. Any of several alternate

so as to form a cone (Fig. 1). Usene into four quarters. Push aside; the remaining two quarters anduartering process until the desired:empt to get a sample of an exact,ple is. wanted, a sample within thebe acceptable.

PRELIMINARY TREATMENTMechanical Sample Splitters

53

A variety of types of mechanical sample splitters are available; themost common type is shown in Fig. 2. Pouring the sample throughthe splitter will divide the sample in half. Replace one of the panscontaining one-half of the sample with a clean pan, and pour this halfthrough the splitter again. The clean pan will then receive one-fourthof the original sample. Repeat as needed to get the desired weight ofsample.

Overloaded sieves do not separate efficiently. If the weight on anyscreen exceeds the values shown in Table 2, a smaller size split of thesample should be obtained and re-sieved.

D A 4. Weigh the split sample to the nearest 0.01 gm. Record onform for recording sieve analysis, line 6 (Fig. 3).

Some workers use a small (about 10 gm) split of the sample anddetermine the moisture content of the sample by heating in a 110°C

d quartering. (After W. S. Tvjer Co.. 1967, Fig. 2 Sample iplitter (From W. S. Tyler Co., 1967, p. 13)

A R3 Q0.81* 8'-

54 SIEVE ANALYSIS

. ii*:v»~ •, !/*- .*™VV-

oven for 2 hours and cooling in a desiccator. The weight of thesample to be sieved is then corrected for the moisture content. Thissupposedly more accurate method, however, may well result in a lessprecise analysis because of the rapid absorption of moisture by thesample between the desiccator and the balance (Folk, 1968, p. 38).

TABLE 2 Maximum sieve loads on 8-in. diameter sieves.Bated on the conservative interpretation, extrapolation,

and combination of the works of Shergold (1946), Whitby (1958),and McManus( 1965).

Sieve Size

Phi mm-2.00 4-1.75-1.50-1.25-1.00 2-0.75-0.50-0.250.00 10.250.500.751.00 1/21.251,501.752.00 1/42.252.502.753.00 1/83.253.503.754.00 1/164.254.504.755.00 1/32

Adjacent1/4 Phi

40 g3634312826242220181716141312111098876655544S

Sieves Differ Bv1/2 Phi I Phi

80 g 160;

68

56 110

48

40 80

34

28 60

24

20 40

17

15

12

10 20

8

7 15

f lR3008l f9

'SIS

desiccator. The weight of the1 for the moisture content. Thisowever, may well result in a less, absorption of moisture by thehe balance (Folk, 1968, p. 38).

on 8-in. diameter sieves,ireution, extrapolation,rgold( 1946), Whitby( 1958).1965).

;nt Sieves Differ By

1/2 Phi80 g

63

56

48

• Q

34

28

24

20

17

15

12

10

8

7

1160 g

110

80

60

40

20

15

REMOVAL OF SUBSTANCES THAT INTERFERE WITH DISPERSAL 55

When using the nonmoisture correction technique, all materialsshould remain exposed to the air until equilibrium is reached withthe moisture in the air.

REMOVAL OF SUBSTANCES THAT INTERFEREWITH DISPERSAL

The decision as to whether or not to remove carbonates, organicmatter, iron oxides, or soluble salts depends on the purpose of theanalysis and the composition of the sample.

SIZE ANALYSIS BY SIEVING

1. Sample No. ____ 2. Analyst___3. Date,of Preliminary Treatment, Dispersal, etc. ____

_4. Summarv

5. Dispersant added________; Concentration____6. Weight of untreated sample _____,——————————————————7. Weight of sample after removal of carbonates, organic matter, ironoxides _,__________________________________________

8. SiPhi

sve Opmm

eningMesh

Grade Size Wt. Retained Weight % Cumulative %

Fig. 3 Form for recording sieve analysis.

3 R 3 Q Q 8 5 Q

.5- V,

56 SIEVE ANALYSIS

Removal of CarbonatesThis procedure is not recommended if mineralogical studies are

be made on the sample.5. Place the sample in a 250- to 600-ml beaker. Add 25 ml distil!

or dcionized water and stir.6. Add 10% HCI slowly until effervescence stops.If carbonate material is abundant, the addition of 10% HCI '.

eventually result in a very large volume of liquid. When the beakenearly full, concentrated acid may be added very slowly or the excliquid may be decanted or siphoned off.

7. Heat to 80 to 90°C. Add HCI until effervescence stops. A mexact procedure is to add HCI until a pH of 3.5 to 4 is reached .maintained. The pH can be checked by using: (a) a pH meter, >tpH indicator solution on a spot test plate (e.g., brom phenol bindicator solution), (c) pH paper. Methyl orange indicator pawhich changes from yellow in a neutral solution to orange at pHto 4.4 and red below pH 3.1 is recommended.

8. If much carbonate material is present, the dissolved calc:ions will interfere with the dispersal of the sample, will hinderremoval of organic matter with the HjOj treatment, andprecipitate as calcium oxalate in the iron removal treatment. Usample with very dilute HCI (about 0.1%). Repeat washing twcthree times. The liquid can be tested for calcium by making a siamount of the liquid in a test tube alkaline to litmus paper \ammonium oxalate. A white precipitate of calcium oxalate will [if much calcium is present.

Washing can be done in several ways: (a) transfer sediment toor more centrifuge tubes using the wash solution in a wash bottle :a -rubber policeman. Stir thoroughly. A rubber stopper smaller tithe inside of the centrifuge tube attached to a glass stirringmakes a good stirrer (Fig. 4). Centrifuge and decant liquid abovesediment cake, (b) If the material is essentially all sand or coarselet the sediment settle in the beaker and decant or siphon offliquid, (c) Place porcelain filter candle in beaker and remove liwith suction or vacuum pump (Fig. 5). The sediment that cakethe filter is removed by applying back pressure.

f lR30085 i

SIS

if mineralogical studies are to

•ml beaker. Add 25 ml distilled

:scence stops.the addition of 10% HC1 will

ne of liquid. When the beaker isadded very slowly or the excessff.ntil effervescence stops. A morea pH of 3.5 to 4 is reached andby using: (a) a pH meter, (b) at plate (e.g., brom phenol blueMethyl orange indicator papertral solution to orange at pH 3.1

Glm rod

Fig. 4 Stirrer for use incentrifuge tubes, grad-uate cylinders, and soon.

, present, the dissolved calciumil of the sample, will hinder thethe HjOj treatment, and willic iron removal treatment. Washt 0.1%). Repeat washing two ord for calcium by making a small>e alkaline to litmus paper withitate of calcium oxalate will form

•ays: (a) transfer sediment to onevash solution in a wash bottle andy. A rubber stopper smaller thanattached to a glass stirring rod

rifuge and decant liquid above thes essentially all sand or coarse silt*ker and decant or siphon off thejidle in beaker and remove liquidg. 5). The sediment that cakes onick pressure. 5 Filtration! using porcelain filter. (From Knunbcin and Pettijohn, 1938,

p. 67)57

-4R300852

58 SIEVE ANALYSIS

.£*v•3i+* f .•' '•**?*•&"

•3*£?;»**-!

T7-' -:: *^»?%Ean^K. -• ,^4«w---»

•5(Vr»»-" - •CTr*r-

—" *' '

'':*feK.r.-

Removal of Organic Matter (Jackson, Whitting, and Pennington.1949, pp. .77-81)

This procedure will seldom remove all the organic matter, but isstill very helpful in dispersing the sediment. This procedure may bestopped after any step, when most of the organic matter has beenremoved.

D 9. If little organic matter is present, place the samp.e in a400-ml beaker and add 100 ml of 6% H2O2 slowly and with constantstirring. Cover and heat to 40°C for 1 hour. Bring to a brief boil atthe end of the heating period to remove excess H2O2 .

10. If much organic material is present, do the following:(a) Remove excess clear liquid by decantation after gravity

settling or centrifuging.(b) Add 30% HjOj very slowly while stirring until frothing

stops. Do not let sample froth over. Avoid contact of skinwith 30% H2O2 , for this reagent will cause bums.

(c) Heat to 40°C on a hot plate for 10 minutes. It may benecessary to remove sample from heat and to cool with ajet of cold water to prevent frothing over. Use a largerbeaker if samples consistently froth over.

(d) Evaporate to a thin paste but not to dryness. Add 10 to30 ml 30% H2O2 > cover with watch glass, and digest at 40to 60° C for 1 to 12 hours. Repeat until organic matter isremoved.

(e) Bring to a brief boil to remove excess H2O2 •

Removal of Iron Oxides (Leith, 1950, pp. 174-176)11. Place sample in a 400-ml beaker and add water to make a.

volume of about 300 ml.12. Place aluminum (a cylinder of sheet aluminum is preferable,

but any form of recoverable aluminum will do) in beaker.13. Add 15 gm oxalic acid, (powder or concentrated solution

containing 15 gm) and boil gently for 10 to 20 minutes. Add moreoxalic acid as needed to remove all the iron.

Removal of Soluble Salts14. Remove- excess liquid by decanting after centrifuging or

gravity settling, or by filtering. If the liquid is turbid with suspended

R R 3 0 0 8 5 3

JALYSIS

kson. Whitting, and Pennington,

>ve all the organic matter, but is.ediment. This procedure may bet of the organic matter has been

present, place the sample in a70 HjOj slowly and with constant>r 1 hour. Bring to a brief boil atiove excess H j O j -•esent, do the following:juid by decantation after gravity

owly while stirring until frothing: froth over. Avoid contact of skinreagent will cause burns.plate for 10 minutes. It may be

iple fr~m heat and to cool with a•even,, othing over. Use a largerently froth over.ite but not to drvness. Add 10 to• with watch glass, and digest at 40jrs. Repeat until organic matter is

cmove excess H2O2 .

1950. pp. 174-176)beaker and add water to make a

• of sheet aluminum is preferable,num will do) in beaker,powder or concentrated solution

.- for 10 to 20 minutes. Add moreI the iron.

decanting after centrifuging orthe liquid is turbid with suspended

DISPERSAL 59

clay, digest by placing tube or beaker containing the sediment in aboiling water bath to cause flocculation. For suspensions that resistflocculation, add a very small amount of NaCl.

15. Wash (see step 8) two to five times. Stop if clay starts todisperse. Recent marine sediments should be washed until chloride-free. A drop of 4% silver nitrate in the filtrate will form a whiteprecipitate of silver chloride if chlorine is present.

If a large number of marine samples are to be processed, removal ofthe salts by dialysis is recommended (Miiller, 1967, pp. 33—34) sothat many samples may be processed at once. Place each sample in adialyzer bag and place in a large container filled with water. Thewater in the container should be changed frequently. Fastest resultsare obtained if water flows continuously through the container. Theprocess may take several days for marine clays.

Drying and Weighing16. Dry sample in air or in a 40°C oven. If no clay is present, the

drying may be done in a 100°C oven. The drying process will bespeeded up if the sample is spread out in a thin layer on a large watchglass, aluminum plate, and so on.

17. Let sample come to equilibrium with the moisture in the roorrair (about 1 hour).

18. Weigh sample to nearest 0.01 gm and record on line 7 of Fig3. This is the weight that is used in calculating percentages afte:sieving.

DISPERSAL

If the sample contains no clay and. little silt, the dispersaprocedure may be eliminated. For accurate work, however, th<sample should be dispersed, for sand grains often have an almosinvisible coating of clay particles. The dispersal procedure shouliresult in the replacement of all exchangeable cations held by the cla-with sodium ions and in the removal of other ions that hindedispersal.

D 19. Place sample in a 400-ml beaker and add 200 ml of distille.or deionized water.

60 SIEVE ANALYSIS

D 20. Add a volume of 10% Calgon equal to we, where w is theweight of the sample and c is the estimated percent of clay. In otherwords, add 1 ml of 10% Calgon for each gram of estimated clay. If indoubt, overestimate the percent clay. Record on line 5 in Fig. 3.Until a person has some experience in estimating the percentage ofclay, it is perhaps advisable to follow the recommendations of ASTMSpecification D422-63 (1963, p. 208) and add a constant 50 ml of10% Calgon to each sample.

The amount of and the kind of dispersing agent that will give thebest dispersal depend on the amount of clay, the type of claymineral, and the kinds of adsorbed ions. Usually this information willnot be known. The work of Rolfe, Miller, and McQueen (1960) hasshown that some clays need an amount of dispersing agent equal to10% by weight of the amount of clay. For best dispersal theoptimum amount of dispersing agent to add must be determined byexperimentation for either too little or too much will decrease theamount of dispersal. Fortunately, the dispersal curve for Calgon has arather broad, flat top, so. that not using the optimum amount ofdispersing agent will not introduce a very large error.

Dispersing agents commonly used are sodium hexametaphosphate(Calgon), sodium tripolyphosphate, tetrasodium phosphate, sodiumcarbonate, sodium hydroxide, sodium oxalate, sodium silicate, andammonia. Ten percent solutions of any of these may be used, butCalgon is usually considered the best overall dispersing agent. Calgonhas the added advantage of complexing calcium ions that may be insolution rather than forming insoluble calcium precipitates, whichthe carbonate and oxalate dispersing reagents do.

D 21. Let soak overnight. Then pour into the dispersion cup of amechanical analysis stirrer (Fig. 6) and mix for 1 to 5 minutes. Afaster but less efficient alternate is to boil the suspension gently for15 minutes and then to mix in the stirrer for 5 minutes (sand) to 30minutes (clay).

For samples that resist dispersal, centrifuge, decant clear liquid,and repeat steps 20 and 21. The decanted liquid will often containthe substances that interfered with dispersal so that the clay willdisperse merely by shaking it in distilled or deionized water.

3n equal to we, where w is themated percent of clay. In other.ch gram of estimated clay. If iny. Record on line 5 in Fig. 3.in estimating the percentage ofthe recommendations of ASTM3) and add a constant 50 ml of

spersing agent that will give theunt of clay, the type of clayns. Usually this information willvliller, and McQueen (1960) hasunt of dispersing agent equal tof clay.- For best dispersal thet to add must be determined bye or too much will decrease thee dispersal curve for Calgon has a: using the optimum amount ofvery large error.

1 are sodium he.tametaphosphate, tet >dium phosphate, sodiumurn oxalate, sodium silicate, andf any of these may be used, butst overall dispersing agent. Calgon:xing calcium ions that may be inluble calcium precipitates, whichg reagents do.pour into the dispersion cup of a) and mix for 1 to 5 minutes. A. to boil the suspension gently for: stirrer for 5 minutes (sand) to 30

d, centrifuge, decant clear liquid,decanted liquid will often containith dispersal so that the clay willstilled or deionized water.

SEPARATION OF FRACTION TO BE SIEVED 61

Fif. 6 Mechanical analysis stirrer.

SEPARATION OF FRACTION TO BE SIEVED

The fraction to be sieved may be separated by wet sieving (steps22-24) or by decantation (steps 25-28).

Separation by Wet SievingD 22. Pour the dispersed sediment onto a wet 1/16-mm screen set

over a large funnel. Make certain that all the sediment has beenwashed from the dispersion cup (use a wash bottle). If the silt andclay are to be analyzed, collect the sediment that passes through thescreen in a 1000-ml cylinder.

O 23. Wash the residue on the screen with distilled or demineral-ized water from a wash bottle. Continue washing until nearly all fines

<£•

3 R 3 G Q 8 5 6

62 SIEVE ANALYSIS

are washed through screen. Do not exceed 1000 ml if the finefraction is to be analyzed.

D 24. Dry sand on sieve in a 110°C oven, over a hot plate or underan infrared drying lamp. The sieve may be damaged if heated higherthan 150°C.

Often the 1/16 mm screens need to be made available for otheruses as soon as possible. An alternate drying procedure is to use awash bottle and transfer the sand on the sieve into a large funnellined with rapid-filtering filter paper. The sand is then dried on thefilter paper.

Let sample remain heated or store in a desiccator until ready forsieving.

Separation by Decantation25. Pour the dispersed sample into one or more test tubes,

centrifuge tubes, high-form beakers, or small graduated cylinders.Stir well and let settle for the time required for a 1/32 mm particleto settle to the bottom (see Table 3).

TABLE 3 Time for quartz particle to settle 10 cm in water3

DiameterPhi44.55

mm1/16

1/32

0.0620.0440.031

012

15°Cmin 32 sec

510

001

Temperature20° C

min 29 sec5755

25°0 min01

C25 sec5142

001

30°Cmin 23

4531

sec

8 For a distance of settling(s) other than 10 cm, multiply above times by j/10.

26. Carefully decant liquid above sediment cake. Collect liquid ina 1000-ml cylinder if the fines are to be analyzed.

27. Transfer .all sediment to one container. Add distilled ordemineralized water (usually 10 cm above the sediment cake). Stirwell. Let settle for required time (see Table 3) and decant. Repeatuntil decanted liquid is clear, usually about five times. After the firstthree settlings, dispersal is often helped by using water adjusted topH 10 with the dispersing agent (about 1 ml of 10% dispersingsolution per liter of water to give a 0.01% solution).

28. Dry sample in a 110°C oven, over a hot plate or under aninfrared drying lamp. The drying time will be decreased greatly if the

3 R 3 0 0 8 5 7

<ceed 1000 ml if the fine

en, over a hot plate or underbe damaged if heated higher

be made available for otherdrying procedure is to use a.he sieve into a large funnelhe sand is then dried on the

i a desiccator until ready for

ito one or more test tubes,or small graduated cylinders,juired for a 1/32 mm particle

to K 10 cm in water"

temperature_____25"C 3<rc

» sec 0 min7 05 I

25 sec 0 min51 042 1

23 sec4531

m , multiply above times by si 10.

cdiment cake. Collect liquid in)e analyzed.e container. Add distilled orabove the sediment cake). Stir

se Table 3) and decant. Repeatabout five times. After the fint

Iped by using water adjusted toabout 1 ml of 10% dispersing01% solution).if over a hot plate or under anie will be decreased greatly if the

SIEVE ANALYSIS 6J

sediment is transferred to a large funnel lined with rapid-filteringfilter paper and the sediment dried on the filter paper. Let sedimentremain heated or store in a desiccator until ready for sieving.

SIEVE ANALYSIS

For efficient sieving the sample must be composed of individualdry grains. According to Bartel (1960, in Muller, 1967, p. 65) with asurface moisture as little as 1%, adhesion forces exist that canovercome the weight of grains smaller than 1 mm.

D A 29. Build up a nest of clean screens for subdivisions desiredwith the coarsest screen on top. Half-height screens will allow a largernumber of screens to be used at one time. A lid should be put on thetop and a pan at the bottom of the nest of sieves.

D A 30. Pour dry sediment onto top screen in nest. Make certainthat all sediment passes the top screen.

Fig. 7 Ro-Tap mechankal shaker. (From W. S. Tyler Co., 1967, p. 15)

64 SIEVE ANALYSIS

D A 31. Place in Ro-Tap mechanical shaker (Fig. 7) and shake for10 minutes.

Most workers have accepted 10 minutes of shaking in a Ro-Tap asan arbitrary standard, although some use 15 minutes. A long shakingtime will result in more material passing through each screen(Whitby, 1958, p. 4); but because of inaccuracies in sieves (Table 1),long shaking times result primarily in the near mesh-size particlespassing through the too-large holes (Muller, 1967, p. 75). The bestsieving is one in which the sum total 4of the inaccuracies caused bythe fines not passing through a sieve and by the coarse materialpassing through oversize holes is the smallest.

D A 32. Empty each sieve onto a large (15 x 15 in.) sheet ofpaper. The removal of sand is helped by striking the rim of the sievewith either the palm of the hand or the wooden handle of a screenbrush along the general direction of the diagonals of the wire meshand brushing the bottom of the sieve with a sieve brush. Use a softbrass wire sieve brush on sieves coarser than 100 mesh. For sievesfiner than 100 mesh, use only a nylon bristle sieve brush. Be carefulnot to push wires apart.

D 33. Add the fines passing the bottom (1/16 mm or smaller)screen to the cylinder containing the fines in step 22 or 26.

D A 34. Weigh each fraction to the nearest 0.01 gm. Makecalculations as shown on Fig. 3. If determined, the weight shown online 7 will be used as the sample weight in determining percentages.

CARE OF SIEVES

D A 35. After each use all sieves should be carefully cleaned (seestep 32) and stored.

36. Occasionally, more thorough cleaning of the screens may beneeded (W. S. Tyler Co., 1967, p. 19).

(a) Wash sieves in warm soapy water using the special sievenylon and brass sieve brushes.

(b) If that treatment fails to remove most of the lodgedparticles,, dip sieves in a boilinjt5% solution of acetic acidand then use sieve brushes on sieves. Wash sieves thor-oughly to remove the acid. - -- ' '

flR3008T9ft

\LYSIS

nicai shaker (Fig. 7) and shake for

minutes of shaking in a Ro-Tap asme use 15 minutes. A long shakingial passing through each screenof inaccuracies in sieves (Table 1),

dy in the near mesh-size particleses (Muller, 1967, p. 75). The best;otal of the inaccuracies caused bysieve and by the coarse material

ic smallest.:o a large (15 x 15 in.) sheet ofped by striking the rim of the sieveor the wooden handle of a screen

. of the diagonals of the wire meshsieve with a sieve brush. Use a softcoarser than 100 mesh. For sievesnylon bristle sieve brush. Be careful

the bottom (1/16 mm or smaller)the ft in step 22 or 26.

to the nearest 0.01 gm. MakeIf determined, the weight shown on

; weight in determining percentages.

ves should be carefully cleaned (see

ugh cleaning of the screens may be>. 19).soapy water using the special sieve

brushes.iils to remove most of the lodgedi a boiling 5% solution of acetic acidbrushes on sieves. Wash sieves thor-acid.

TESTING SIEVES 65

ACCURACY OF SIEVES

Three different types of sieves may be purchased. Most commer-cially available sieves are manufactured to meet the tolerancesestablished under ASTM Specifications Ell-61. (See Table 1.) TheNational Bureau of Standards will, for a fee, check a set of sieves andwill certify them if they meet ASTM specifications. The manufac-turer selects matched sieves to give results for a given sample that arecomparable to those obtained from the manufacturer's Master Sieves.Matched sieves are the most accurate available.

TESTING SIEVES

Sieves may be checked for accuracy in several different ways(ASTM, 1966, and W. S. Tyler Co., 1967, p. 39).

Use of Standard SamplesThe use of calibrated glass spheres is recommended for checking

and determining the effective sieve openings. Calibrated glass spheresmay be obtained from the Supply Division, National Bureau ofStandards, Washington, D. C. Three standard samples are nowavailable at $9.50 each: No. 1017, 0.050 to 0.230 mm; No. 1018,0.210 to 0.980 mm; and No. 1019, 0.90 to 2.55 mm. Instructionsare provided for using the glass spheres in calibrating sieves.

For routine checking of sieves each laboratory should maintain itsown standard sample. A set of sieves should be checked periodicallywith a standard size split of the standard- sampfe to see if the setcontinues to give^e same results, A next set of sieves- can also bechecked against the standard to see if the sets give- comparableresults. If they do not, calibration factors can be calculated for eachsieve that will make the results comparable.

Measurement of OpeningsSeveral methods of measuring openings are given in ASTM

Specification £11-61. One method is to use a microscope and measurethe openings. Six nonoverlapping fields of view are selected. In each

f lR3008-60

66 SIEVE ANALYSIS

field measure at least 50 openings perpendicular to the wires, withthe openings being'located in a diagonal direction across the field(Fig. 8). The openings in three of the fields should be measured atright angles to those in the other three fields. Tabulate the resultsand check against Table 1.

REFERENCES

American Society for Testing Materials, 1963, Grain size analysis ofsoils, D422-63, pp. 203-214, in 1967 Book of ASTM Stand-ards, Pt. 11, Philadelphia.

———, 1966, Sieves for testing purposes, Ell-61, pp. 446—452, in1966 Book of ASTM Standards, Pt. 30, Philadelphia.

Folk, R. L., 1968, Petrology of sedimentary rocks, Hemphills,Austin, Texas, 170 pp.

Jackson, M. L., L. D. Whitting, and R. P. Pennington, 1949,

Fig, ft Jetting sieve* by micxotcopie measurement of opening* located alongdiagonalrof opeaingg.

f t R 3 Q Q 8

LYSIS

rrpendicular to the wires, with.3nal direction across the fielde fields should be measured atree fields. Tabulate the results

ils, 1963, Grain size analysis ofi 1967 Book of ASTM Stand-

3oses, Ell-61, pp. 446-452, in't. 30, Philadelphia,sedimentary rocks, Hemphills,

and R. P. Pennington, 1949,

uurement of openings located along

REFERENCES 67

Segregation procedures for mineralogical analysis of soils, SoilSci. Soc. Am. Proc., 14, 77-81.

Krumbein, W. C. and F. J. Pettijohn, 1938, Manual of sedimentarypetrology, Appleton-Century-Crofts, 549 pp.

Leith, C. J., 1950, Removal of iron oxide coatings from mineralgrains,/. Sed. Pet., 20, 174-179.

McManus, D. A., 1965, A study of maximum load for small diameterscreens,/. Sed. Pet., 35, 792-796.

Mliller, German, 1967, Sedimentary petrology, Part I, Methods insedimentary petrology, translated by Hans-L'lrich Schmincke,Hafner Publishing Co., 283 pp.

Rolfe, B. N., R. F. Miller, and I. S. McQueen, 1960, Dispersioncharacteristics of montmorillonite, kaolinite, and illite clays inwaters of varying quality and their control with phosphatedispersants, U.S. Geol. Surv. P.P. 334-^G, pp. 229-273.

Shergold, F. A., 1946, The effect of sieving loading on the results ofsieve analysis of natural sands, Soc. Chemical Industry Trans., 65,245-249.'

Whitby, K. T., 1958, The mechanics of fine sieving, pp. 3-24, inSymposium on particle size measurement, ASTM Spec. Publ. No.235, Philadelphia, 303 pp.

W. S. Tyler Co., 1967, Testing sieves and their uses (Handbook 53),W. S. Tyler Co., Mentor, Ohio, 48 pp.

A R 3 Q 0 8 6 2

(TIG & ALLARDCCE

i giycerol and ethyiene

>r the identification of

•s for X-ray diffraction

- idards for quantitative11400-406.ondon.

13 Bulk Density1

G. R. BLAKEUniversity of MinnesotaSt. Paul, Minnesota

K. H. HARTGEUniversity of HanoverHanover, Federal Republic of Germany

13-1 GENERAL INTRODUCTION

Soil bulk density, p», is the ratio of the mass of dry solids to the bulkvolume of the soil. The bulk volume includes the volume of the solidsand of the pore space. The mass is determined after drying to constantweight at 105 "C, and the volume is that of the sample as taken in thegeld.

Bulk density is a widely used value. It is needed for converting waterpercentage by weight to content by volume, for calculating porosity andvoid ratio when the panicle density is known, and for estimating theweight of a volume of soil too large to weigh conveniently, such as theweight of a furrow slice or an acre-foot

Bulk density is not an invariant quantity for a given soil. It varieswith structural condition of the soil, particularly that related to packing.For this reason it is often used as a measure of soil structure. In swellingsoils it varies with the water content (Hartge, 1965, 1968). In such soils,the bulk density obtained should be accompanied by the water contentof the soil at the time of sampling.

The determination usually consists of weighing and drying a soilsample, the volume of which is known (core method) or must be deter-mined (clod method and excavation method). These methods differ inthe way the soil sample is obtained and its volume determined. A differentprinciple is employed with the radiation method. Transmitted or scat-tered gamma radiation is measured; and with suitable calibration, thedensity of the combined gaseous-liquid-solid components of a soil massis determined. Correction is thflp necessary to remove the componentsof density attributable to liquidlnd gas. that are present The radiatioamethod is an. in. situ method. . _ - . _ • •

'Piptr no. 11718 of the Scientific Journal Series, MinnesoUrAjrieultual ExperimentStation, Si Piui, MN.Copyright 1986 C American Society of Agronomy—Soil 3ct«nc» Society of America. 677South Setot Road, Madiion. WT 5371 r. USAi Method of Soit Analysis, Pan I. Physicaland Mintniogicat Methods— Agronomy Monograph no. 9 (2nd Edition)

343

HR300863

were developed in rcceni /cars, cnieuy uj sou engineers torbituminous and gravelly material. More recently the excavation methodhas found use in ullage research, or where surface soil is often too looseto allow core sampling, or where abundant stones preclude the use ofcote samplers. Radiation methods have been used since the 1950s, par-ticularly in soil engineering.

Bulk density is expressed in SI units or units derived from them. Themost straightforward would be kg m"3. However, derived units such astons m"3, g cm"1, or Mg m~}, which are numerically equal to each other,may be more convenient, as they give values for soils which vary fromabout 1.2 to 1.7 (rather than from 1200 to 1700, as when units of kg nrj

are used). Obsolete terms such as "volume weight" (weight • volume"1)and "bulk specific gravity" or "apparent specific gravity" are sometimesfound in the older literature and in some foreign language literature.Specific gravity terms are relative densities, i.e. density of a substancewith respect to water at 4°C, and are nearly equal numerically to bulkdensity. At standard gravitation (g - 9.8 m s"2), kilogram weight andkilogram mass are equal, and under this condition "volume weight" isnumerically equal to bulk density. In many engineering and commercialapplications, bulk density is expressed in Ib ft"3, which one may convertto g cm"3 by dividing by 62.4 (which is the mass, in pounds, of a cubicfoot of a substance whose density is unity, i.e., water at 4 *C).

13-2 CORE METHOD

13-2.1 Introduction

With this method, a cylindrical metal sampler is pressed or driven*into the soil to the desired depth and is carefully removed to preserve aknown volume of sample as it existed in situ. The sample is dried to105 "C and weighed. The core method is usually unsatisfactory if morethan an occasional stone is present in the soil.

13-2.2 Method

Core samplers vary in design from a thin-walled metal cylinder to acylindrical sleeve with removable sample cylinders that fit inside. Sam-piers are usually designed not only to remove a relatively undisturbedsample of soil from a profile, but also to hold the sample during transportand eventually during further measurements in the laboratory, such aspore-size distribution or hydraulic conductivity. For the latter measure-ment it is desirable to have core diameters not less than 75 mm andpreferably 100 mm to minimize the effect of disturbed soil interfacingthe cylinder wall. For the same reason it is desirable that the height ofthe cylinder not exceed the diameter.

fitted one insideinner to accept aedge at the loweidiameters of thethe lower end, thsurface of the outable in slightly diServices, UMC 1

Where densiimined, one can o\on a pickup trucisoil and removecslit running mosta rounded knifeSegments typicaland placed in cothe probe model,tensions for greatare **• maole froiSt.. • lollinsStreet, Cmckashs60202.

Fit. 13-i. Typical dofor bulk density.

f lR3-0086l*

SLAKE <fc HARTGE BULK DENSITY 365

/ years. Excavationsoil engineers for

excavation methodil is often too loosejreclude the use of

• nee the 1950s, par-

•ed from them. Therived units such as:qual to each other,Is which vary fromien units of kg m~J

weight • volume'1)ity" are sometimeslanguage literature.sity "e a substance

illy to bulkm weight andme weight" is

nd commercial'one may convert

pounds, of a cubic• at 4 °C).

; pressed or drivenoved to preserve asample is dried to.atisfactory if more

metal cylinder to alat fit inside. Sam-tiveiy undisturbedle during transportaboratory, such as

*1he' *r measure-tha». 5 mm and

ed soil interfacingthe height of

ifi

A. widely used and very satisfactory sampler consists of two cylindersfitted one inside the other. The outer one extends above and below theinner to accept a hammer or press at the upper end and to form a cuttingedge at the lower. The inside cylinder is the sample holder. The insidediameters of the two cylinders when nested are essentially the same atthe lower end, the inner being fitted against a shoulder cut on the innersurface of the outside cylinder. Figure 13-1 shows such a sampler (avail-able in slightly different design from the Utah State University TechnicalServices, UMC 12, Logan, UT 84322).

Where densities at various depths in a soil profile are to be deter-mined, one can obtain samples with a hydraulically driven probe mountedon a pickup truck, tractor, or other vehicle. The probe is forced into thesoil and removed hydrauiicaily. The probe tube has a 2- to 3-cm wideslit running most of the length of the tube, through which one can inserta rounded knife or spatula to slice off segments of the soil as desired.Segments typically 10 cm in length are cut and removed from the tubeand placed in containers for transport to the laboratory. Depending onthe probe model, samples can be taken to about l-m depth, though ex-tensions for greater depths are available for many models. Probe samplersare available from Giddings Machine Co., P.O. Drawer 2024, 401 PineSt., Fort Collins, CO 80522; A. D. Bull Enterprizes, 1904 South 21stStreet, Chickasha, OK 73018; or Soiltest Inc., 2205 Lee St., Evanston, IL60202.

Ft*. lisLTypial douhto-eytiader,tot bulk 4fBtit

romunpter, for obttiniat soil samples-'

Jf lR300865

Numerous hand-driven samplers have been described in the litera-ture. Some of the more accessible ones are described by Lutz (19471,Jamisonetal. (1950), and U.S. Department of Agriculture (1954, p. 159).Mclntyre (1974) describes types of core samples and their properties andgives additional references,

13-U.l PROCEDUREThe exact procedure for obtaining the samples depends on the kind

of sampler used. The following steps apply when the widely known dou-ble-cylinder sampler is used.

Drive or press the sampler into either a vertical or horizontal soilsurface far enough to fill the sampler, but not so far as to compress thesoil in the confined space of the sampler. Carefully remove the samplerand its contents so as to preserve the natural structure and packing ofthe soil as nearly as possible. A shovel, alongside and under the sampler,may be needed in some soils to remove the sample without disturbance.Separate the two cylinders, retaining the undisturbed soil in the innercylinder. Trim the soil extending beyond each end of the sample holder(inner cylinder) flush with each end wuh a straight-edged knife or sharpspatula. The soil sample volume is thus established to be the same asthe volume of the sample holder. In some sampler designs, the cuttingedge of the sampler has an inside diameter slightly less than the sampleholder, so as to reduce friction as the soil enters the holder. In these cases,determine the diameter of the cutting head and use this to calculate thesample holder volume. Transfer the soil to a container, place it in anoven at 105 °C until constant weight is reached, and weigh it. The bulkdensity is the oven-dry mass of the sample divided by the sample volume.

13-12.2 COMMENTSIt is not necessary that soil be kept undisturbed during transport to

the laboratory and drying. A single sample cylinder can be reused if eachsample is transferred to another container. It is often desired, however,to make other measurements such as pore-size distribution, conductivity,or water retention in addition to bulk density on the same samples. Theserequire that they be kept undisturbed, each sample being transported inthe sample cylinder in which it was taken. Thus one must provide forsufficient cylinders. Frequently other measurements to be made in thelaboratory require that samples be kept at field water-content In thatcase cylinders must be placed in containers that do not permit loss ofwater during transport Waxed paper or plastic containers with lids aresatisfactory for this purpose.

Core samples should be taken in soils of medium water content Inwet soils, friction along the sides of the sampler and vibrations due tohammering are likely to result in viscous flow of the soil and thus incompression of the sample. When this occurs the sample obtained isunrepresentative, being more dense than the body of the soil. Compres-

sion may occursis taken, one shethe sampler is thOne can only rotsample is changi

In dry or harethe sample, and •<.the sampler intcshattering. Closeestimate whethesoils, soil level i.the sample is to

Bulk densityof soil, drying acavation. In thethe hole with sarubber-balloon rinto the excavaicavation is justequal to the voldone it is possivolume. Mensumine the volurr

i:13-3.2.1 SPEC

13-3.2.1.1.2205 Lee Street1. A metal rum

on the stemsand contair

2. A standards.be fairly uniconsequent >and retainec

3. A template csquare, with

4. Scales to we

f lR300866

HARTGE BULK DENSITY 367

the litera-uz (1947),

_54, p. 159).:erties and

n the kindnown dou-

zontal soilmpress theic samplerpad ' of

Ji. er,rbance.e inner

iple holderfe or sharpIB same asthe cuttingthe sample:hese cases,ilculate thece it in an:. The bulkile volume.

^/aw.

•

-ansport toised if eachI, however,nductivity,pies. Theseisported injrovide for\ade in thent. In thatmit loss ofith are

intent. Ins due. tothus m

obtained is. Compres-

sion may occur even in dry soils if they are very loose. Whenever a sampleis taken, one should carefully observe whether the soil elevation insidethe sampler is the same as the undisturbed surface outside the sampler.One can only roughly estimate in this manner whether the density of thesample is changing because of sampling.

In dry or hard soils hammering the sampler into the soil often shattersthe sample, and an actual loosening during sampling may occur. Pressingthe sampler into the soil usually avoids the vibration that causes thisshattering. Gose examination of the soil sample usually allows one toestimate whether serious shattering occurs. And, as in the case of wetsoils, soil level inside and outside the sampler must remain the same ifthe sample is to be considered satisfactory, (see also Mclntyre, 1974.)

13-3 EXCAVATION METHOD

13-3.1 Introduction

Bulk density is determined in this method by excavating a quantityof soil drying and weighing it, and determining the volume of the ex-cavation. In the sand-funnel method, the volume is determined by fillingthe hole with sand, of which the volume per unit mass is known. In therubber-balloon method, the volume is determined by inserting a ballooninto the excavation and filling it with water or other fluid until the ex-cavation is just full The volume of the excavated soil sample is thenequal to the volume of the fluid dispensed. If the excavation is carefullydone it is possible simply to measure its dimensions and calculate thevolume. Mensuration apparatus is described that enables one to deter-mine the volume of an irregular excavation.

13-3.2 Method (ASTM, 1958, p. 422-441)

13-3.2.1 SPECIAL APPARATUS13-3.2.1.1. Sand-Funnel Apparatus (see Fig. 13-2) (Soiltest, Inc.,

2205 Lee Street, Evanston, IL 60202).&•1. A meul funnel 13 to 18 cm at its largest diameter, fitted with a valve

on the stem. Attached to the stem when the funnel is inverted is asand container.

2. A standard sand that is clean, dry, and free-flowing. Particle size shouldbe fairly uniform to avoid possible separation in the dispenser withconsequent error in calibration. Sand particles passing a no. 20 sieveand retained on a no. 60 steve are recommended (0.841-0.25 mm).

3. A template consisting of a thin, flat, metal plate approximately 30 cmsquare, with a hole 10 to 11 cm in diameter in its centerr

4. Scales to weigh to 5 g.

H R 3 G Q 8 6 7

BLAKE & HASTGE

•.*

Fit. 13-2. Apparatus for sand-funnel technique of determining soil bulk density in place.

13-3.2.1.2. Rubber-Balloon Apparatus.1. A thin-walled rubber balloon (may be purchased from Barr Inc., 1531

First Street, Sandusky, OH 44870, and the Anderson Rubber Co., 310-T N. Howard Street, P.O. Box 170 Akron. OH 44309).

2. A 1000-cm3 graduated cylinder and a water container.3. A template, described in section 13-3.2.1.1 (3).

Rubber-balloon density apparatus is available from several manu-facturers supplying soil testing equipment. {One-supplier is Soiltest, Inc.,2205 Lee Street, Evanston. IL 60202.) The apparatus made commerciallyhas the convenience of a volumetrically calibrated water container-dis-penser, with suction facilities for returning the water to the container forre-use (Fig. 13-3).

13-3.2.1 J Mensuration Apparatus.1. Tape measure marked in millimeters.2. Flat metal plate approximately 50 cm square, with 30 to 40 evenly

spaced holes forming a grid through which the tape measure can beinserted. Alternatively, 3 wooden beams 3 by 3 by 80 cm with 5-cramarkings may be used.

3. Four wood stakes approximately 10 cm long, one end sharpened.4. Scales to weigh to approximately 10 g.

13-3.12. PROCEDURE13-3.2.2.1. Sand-FmniMl Procedure. Level the soil surface and re*

move loose soil at the test site. Place the template on the soil Excavatea soil sample through the center hole of the template, leaving a hole witha diameter of approximately 12 cm and a depth of approximately 12 cm,

8LLX J£>5IT

Fig. 13-3. Apparmque.

or other valuRecover all eloose soil thaithe oven-dryweighing it.

Determinlevel of the bnecessary, buflowing sand,plate, as is doilem ofievelinfree flow of sbeing subtrac

Determinweighing it tcsand by lettirflow as in the tfrom it, detenof sand dispe;

13-3.2.2.:the template •the precedingthe balloon vvolume of wamarkings toplaced on a h

A HARTGE BULK DENSITY 369

fensity in place.

Barr Inc., 1531ubberCo., 310-

several manu-is Soiltest, Inc.,e commerciallyr container-dis-ne container for

30 to 40 evenlymeasure can beD cm with 5-cm

d sharpened.

rface and re-ill. Excavate

ving a hole withiximately 12 cm.

Fig. 13-3. Apparatus for determining soil bulk density in place by the rubber-balloon tech-nique.

or other, value as desired. A large spoon is convenient for excavating.Recover all evacuated soil in a container, being careful to include anyloose soil that has fallen in from the sides of the excavation. Determinethe oven-dry soil mass including, stones by drying the soil to 10S °C andweighing it

Determine the volume of the test hole by filling it with sand to thelevel of the bottom of the template. Level the sand with a spatula ifnecessary, but disturb it as little as possible to avoid packing the free-flowing sand. (Dispensing the sand through a funnel placed on the tem-plate, as is done with commercially available equipment, avoids the prob-lem of leveling the sand. The excavation as well as the funnel is filled byfree flow of sand, the predetermined weight required to fill the funnelbeing subtracted as a tare,)

Determine the weight of sand required to fill the test excavation byweighing it to the nearest 5 g. Precalibrate the mass-to-volume ratio ofsand by letting sand fall from a similar height and at a similar rate offlow as in the test procedure. Using the calibration curve or values derivedfrom it, determine the volume of the excavation from the measured massof sand dispensed*

13-33.2.2. Rnbbcr-Balloe* Proctdv*. Level the soil surface, placethe template on the surface, and excavate a soil sample as described inthe preceding section. Place the rubber bgtoon in the test hole and fillthe balloon with water to the bottom offlfe template. Determine thevolume of water required to the nearest 2 cm1. (A 1000-cm3 graduate hasmarkings to 10 cm1, but one can estimate to 2 cm1 if the graduate isplaced on a horizontal surface.)

H R 3 G Q 8 6 9

370 BLAKE * HAATCE

i

Calculate bulk density from the oven-dry mass of the excavated sam-ple and the volume of the test excavation.

13-3.2.2.3. Mensuration Procedure. Prepare the soil surface as de-scribed in previous procedures. Drive wooden stakes into the soil at fourcorners of a square about 40 cm on a side, allowing them to project 1 to3 cm above the soil surface. Place the metal plate on the stakes. Measurethe distance from the upper surface of the plate to the soil surface througheach of the holes. Remove plates and excavate soil from an area about30 by 30 cm to a depth of 10 cm. Weigh the soil including stones. Removean aliquot of reasonable size for determination of water content anddiscard the remainder. Replace the plate on the stakes and measure thedistance from the top of the plate to the excavated surface through eachof the holes as before.

If wooden beams are used in place of a metal plate, place two beamsparallel, each resting on two stakes. With the third beam, bridge acrossthe other two and from this datum, measure distance to the soil surfaceon a 5-cm grid using care that the tape is perpendicular to the beam. Asabove, excavate the soil sample and again measure distance from thethird beam to excavated soil surface on a 5-cm grid. Weigh the soilincluding stones. Remove an aliquot for water-content measurement anddiscard the remainder of the excavated soil.

Calculate bulk density, p*, from the weight of the soil corrected tooven dryness and the volume of the excavated soil. The volume is de-termined by summing the volumes around each depth measurement asfollows:

V - (Id - SdoM

whered ™ depth after excavation,

do » depth before excavation, andA - area covered by each measurement of the ruler. If holes are on

5-cm centers in the plate or measurements are made at 5-cmcenters with the wooden beams, A - 25 cm1.

By subsequent excavation of deeper layers in the same holes, one candetermine bulk density deeper in the profile by measurements from thesame datum.

13-3.2J COMMENTSBulk density can be estimated accurately by excavation methods car-

ried out carefully. Holes should have smooth, rounded walls. Protrudingstones should be included in the sample, care being used to round andsmooth the area from which stones are taken. A heavy pair of scissorscan be used to cut roots at the wall surface so the surrounding soil isundisturbed.The relatively large sample (a cylinder of 12-cm diameter and of 12-cm depth- has a volume of 1357 cm1) has the advantage that small errors

BLTJC DENSITY

Ttbl«L3-l. C

Soil maUnal

Brown Mnd. trie* »Brown silt and ctiyBrownsmadandgri

aom* silt, trie* clBrown till

Brown sand, trie* ;Brown lilt tad clayBrown sand and gr

somt silt, trace clBrown till_____t A positive valui i

in measuring wadvantage is theof 5 cm3 in liqua bulk density 01to perhaps 2 en-arises in deterrrbottom of the teThe volume ofa considerablyneglected.

An error olbulk density islikely to resultlevel at the botresult in an errrequired to assvfor the dispens

If one assurmethod and mmulative errorvolume measu:

A compari:by Mintzer(l9

The bulktheir mass am

f lR300870

ILAKE <fc HAKTGE

; excavated sam-

nl surface as de-o the soil at four•n to project 1 tostakes. Measure

' 1 surface through-n an area about. stones. Removeiter content andand measure theice through each

place two beamsm, bridge across> the soil surfaceto l*- beam. Asstan rom the

reigh the soillUrement and

soil corrected toie volume is de-measurement as

If holes are on; made at 5-cm

e holes, one can•ments from the

on methods car-alls. Protrudingd to round and

* pair ~f scissors-out. j soil is

and of 12-small errors

BULK DENSITY

Table 13-1. Comparison of surface nuciMr gauge tnd sand-con* method fordetermining soil bulk density (Mintzer. 1961).

371

Soil material

Brown sand, eric* siltBrown silt and dayBrown sand and gravel

some silt, trace clayBrown till

Brown sand, trace siltBrown silt and clayBrawn sand and gravel

some silt, trace clayBrown till

Number ofcomparisons

Wet bulk density, *.94

64

Dry bulk density, p»94

a4

Meandifference

2.030.39

1.01-1.19

2.057.21

1.48-0.38

Extremedifference

-0.25-4.28-0.64-1.87

-2.27-7.75-3.97-1.60

-1.21-4.985.51-9.27

-1.71-8.32-4.53-3.21

t A poeitive value indicates nuclear method gave higher bulk density value.

in measuring water volumes or sand weights are insignificant The dis-advantage is the lack of discrimination to a localized horizon. An errorof 5 cm1 in liquid volume will give an error of 0.005 in a sample havinga bulk density of 1.36 g cm ~3. Though one determines the water dispensedto perhaps 2 cm1, a much greater source of error in water measurementarises in determining when the water in the excavation is level with thebottom of the template. Extreme care and judgment are required in this.The volume of the balloon itself, being of the order of 2 cm3, will givea considerably smaller error than the volume measurement, and can beneglected.

An error of 7 g in weighing the sand gives an error of 0.005 if thebulk density is 1.36 g cm "3. As in the balloon technique, greater error islikely to result in the precision with which one can determine the sandlevel at the bottom of the template. An error of 1 mm in this level willresult in an error of 0.01 in the bulk density. Extreme care is thereforerequired to assure that the sand level is at the template bottom. The needfor the dispensing runnel in reducing this error is obvious.

If one assumes an excavation of 30 by 30 by 10 cm in the mensurationmethod and measures depth 36 times on a 5-cm grid, assuming a cu-mulative error of 1 mm in each of the depth measurements the error involume measurement is 1%.

A comparison of the sand-funnel and radiation methods was madeby Mintzer (1961), and the results are summarized in Table 13-1.

13-4 CLOD METHOD

13-4.1 Introduction

The bulk density of clods, or coarse peds, can be calculated fromtheir mass and volume. The volume may be determined by coating a

H R 3 Q Q 8 7 1

372, --.t»X.g,, l r tAiW».

clod of known weight with a water-repellent substance and by weighingit first in air. then again while immersed in a liquid of known density,making use of Archimedes' principle. The clod or ped must be sufficientlystable to cohere during coating, weighing and handling.

13-4.2 Method

13-4.2.1 SPECIAL APPARATUS1. A balance, modified to accept the clod suspended below the balance

arm by means of a nylon thread or thin wire, to allow weighing theclod when it is suspended in a container of liquid.

2. A fine nylon thread or 28 to 30 gauge wire, to attach the clod to thebalance. A fine nylon hairnet makes a good container for the clod.

3. Saran solution. Dissolve 1 part by weight of Saran resin (Dow SaranF-310; Dow Chemical Co., Suite 500/ Tower No. 2, 1701 West GolfRoad, Rolling Meadows, IL 60008) in 7 parts by weight of methylethylketone in a 1-gallon container in sufficient quantities to fill the con-tainer about three-quarters full. Manufacturer's instructions for safehandling of solvents should be carefully followed. Dissolution requiresabout an hour, with vigorous stirring. Since the solvent is flammableand explosive when its vapors are mixed with air, either hand-stirringor use of an air-driven stirrer should be employed in a well ventilatedhood. The solution can be stored for long periods if kept in a tightlyclosed container to prevent evaporation of the solvent.

13-4.2.2 PROCEDURESecure the clod with two loops of the thread or wire, loops being at

right angles to one another, leaving sufficient thread or wire to connectto the balance arm. Weigh the clod and thread. Holding it by the thread,dip the clod into the saran solution. Suspend it in air under a hood for15 to 30 min to allow the solvent to evaporate. Repeat dipping and dryingone or more times as needed, to waterproof the clod. Weigh the clod,with its coating and the thread. Weigh it again when it is suspended inwater and note the water temperature. Determine the tare weight of thethread or wire. To obtain a correction for water content of the soil, breakopen the clod, remove an aliquot of soil, and weigh the aliquot beforeand after oven-drying it at 105 °C.

Calculate the oven-dry mass of the soil sample W^ as follows, fromthe water content of the aliquot removed from the clod after other weightsare taken:

W^ - WJ(\ + 0.)

where 9 - water content of the subsample in g/g andof clod or ped in air at its original water content.

Calculate bulk density as follows:

where

13-4.2.3 C

The clcother methnot take th

Extremof soil. Clo<for these aisoil masses

I fbubbor if the v,clod, and t.

Brashe:gested that1 part resingave the de

Precisitfor the diffcthe error is

Using <gives a staisingle meaiby using laa greater nstandard d<

Severaiincluding p

- net weightThetra

soil variesbration, mradiation c

SLAKE 4 HARTCE

and by weighingf known density,ast be sufficiently

BULK DENSITY 373

elow the balancelow weighing the

h the clod to theer for the clod,-esin (Dow Saran, lYO! West Golf.htofmethylethyles to fill the con-tractions for safessolution requires,-ent ammable

hand-stirringventilated

•ept in a tightlyent.

/em

^Wfep

~ ire. loops being ator wire to connectig it by the thread,- under a hood fordipping and dryingi. Weigh the clod,it is suspended intare weight of thet of the soil, breakthe aliquot before

di as follows, fromafter other weights

W„ • net weight

whereP.ool

P»

- density of water at temperature of determination,— oven-dry weight of soil sample (clod or ped),— net weight of clod or ped in air,— net weight of soil sample plus saran in water,- weight of saran coating in air, and* density of saran.

13-4.2J COMMENTSThe clod method usually gives higher bulk-density values than do

other methods (Tisdall, 1951). One reason is that the clod method doesnot take the interclod spaces into account

Extreme care should be exercised to get naturally occurring massesof soil. Gods on or near the soil surface are likely to be unrepresentative,for these are often formed by packing with tillage implements. Naturalsoil masses, or coarse peds, that are more representative should be sought

If bubbles appear on the saran when the sample is weighed in wateror if the weight in water increases with time, water is penetrating theclod, and the sample must be discarded.

Brasher et al. (1966) first proposed use of saran coating. They sug-gested that for clods with large pores, a more viscous saran solution of1 pan resin to as little as 4 parts methylethy! ketone could be used. Theygave the density of saran to be 1.3 g cm"3.

Precision in calculating the bulk density would require a correctionfor the difference of the weight of the wire in air and in water. However,the error is negligible with thread or a 28-gauge wire.

Using clods as small as 40 g oven-dry weight and weighing to 10 mggives a standard deviation in the bulk density with 25 replications of asingle measurement of 0.07 g cm"1 (Hartge, 1965). This can be reducedby using larger clods or by weighing to 1 mg or both. Obviously, usinga greater number of samples for a determination would also reduce thestandard deviation.

Several other substances have been used to seal the clod against water,including paraffin, rubber, wax mixtures, and oils.

13-5 RADIATION METHODS

13-5.1 Introduction

The transmission of gamma radiation through soil or scattering withinsoil varies with soil properties, including bulk density. By suitable cali-bration, measurements of either transmission or scattering of gammaradiation can be used to estimate bulk density.

!:

il

& R 3 Q 0 8 7 3

374

II

li

i l l ,

i « 'I '-I t

.( iI 1

HAKTGEIn the transmission technique, two probes at a fixed spacing are low-

ered into previously prepared openings in the soil. One probe containsa Geiger tube, which detects the radiation transmitted through the soilfrom the gamma source located in the second probe. The scattering tech-nique employs a single probe containing both gamma source and detectorseparated by shielding in the probe. It can be used either at the soil surfaceor placed in a hole, depending on design of the equipment

Radiation methods have several advantages, among which are min-imum disturbance of the soil, short time required for sampling, acces-sibility to subsoil measurement with minimum excavation, and the pos-sibility of continuous or repeated measurements at the same point.

Both transmission and scattering techniques measure the bulk densityof all components combined. The densities of gaseous components areinsignificant in comparison to those of the solid or liquid components,and can therefore be ignored. It is necessary, however, to determine thewater content of the soil at sampling time and to apply a correction toobtain bulk density on a dry soil basis.

13-5.2 Methods

13-5.2.1 SPECIAL APPARATUS

Transmission apparatus is supplied by Troxler Electronics Labora-tories, P.O. Box 12057, Cornwallis Road, Research Triangle Park, NC27709, following a design by Vomocil (1954). A design, including a dis-cussion of the theory of the method, calibration, and methods of makingmeasurements was included in the first edition of Methods of Soil Anal-ysis, Part 1 (Blake, 1965).

Scattering apparatus is supplied by Troxler Electronic Laboratories,P.O. Box 12057, Comwailis Road, Research Triangle Park, NC 27709and by Soiltest Inc., 2205 Lee Street, Evanston, IL 60202.

13-5.2.2 PROCEDUREIt is recommended that the instructions supplied with the commercial

apparatus be followed. One may also wish to refer to the first edition ofMethods of Soil Analysis, Part I (Blake, 1965).

13-5.2-3 COMMENTSThere is some radiation hazard with these methods. Gamma photons

are high-energy radiation. Some will pass through several centimeters oflead shielding. Commercially available equipment, as well as designs de-scribed in the literature, reduce the hazard to safe levels. But it is im-.portant to adhere strictly to time limits, distances, and other conditionsdescribed by the manufacturers. One should be equipped for and knowl-edgeable in means of checking the equipment for radiation levels ac-

BLTUi

cordinequipr

Siion prctwo-prexacth

Mand thcompesurfaciwas u«

\m. SoMs

Blake.I.

Brasherto .Sci

Hanie,

Hame,5th

JamisoiSot

LUO.J.Mclnty

d«SOLFu

Mintzodetme54.

TisdalLJ.

U. S. Isoi

Vomoc

.AKE £ HARTGE

pacing are low-probe containshrough the soilscattering tech-•ce and detector

_ the soil surface•nt.which are min-ampling, acces->n, and the pos-ame pointthe bulk density:omponents areid components,j determine thea correction to

BULK DENSITY 375

tronics Labora-..angle Park, NC-including a dis-hods of makingds of Soil Anal-

c Laboratories,ark, NC 27709

the commercial: first edition of

cording to the way it is handled in actual sampling. If there is doubt, theequipment should be checked for safety by a competent testing laboratory.

Since radiation transmitted from a source to a detector is dependenton probe spacing or sample thickness, care must be exercised with thetwo-probe sampler to assure that access holes are parallel and spacedexactly as in the calibration.

Mintzer (1961) reported comparisons of the surface-density probeand the sand-cone method on four engineering projects. He reported hiscomparisons on both the wet and dry bulk-density bases. He used asurface neutron meter for water content where the surface-density probewas used. His results are summarized in Table 13-1.

13-6 REFERENCES

Am. Soc. Test. Mater. 1958. Procedures for testing soils. American Society for Testing andMaterials, Philadelphia.

Blake, G. R. 1965. Bulk density. In C A. Black et ai (ed). Methods of soil analysis. Pan1. Agronomy 9:383-390.

Brasher. B. R., 0. P. Franzmeier. V. Valassis. and S. E Davidson. 1966. Use of Saran Resinto coat natural soil clods for bulk density and moisture retention measurements. SoilSci 101:101.

Hartge, K. H. 196S. Vergjeich der Schrumpfung ungestorter Boden und gekaeteter Fasten.zTFriedr. Wilh. Univ. Jena, (math-nat. Reihe) 14:53-57.

Hartge, K. H. 1968. Heterogenitat des Bodens Oder Queilung? Trans. Int. Congr. Soil Sci..3:591-597.

Jamisoo, V. C, H. H. Weaver, and L F. Reed. 1959. A hammer-driven soil core sampler.Soil ScL 69:487-496.

Lutz, J. F. 1947. Apparatus for collecting undis d soU simples. Sod Sci. 64:399-401.Mclnryre, O. S. 1974. Soil sampling techniques for physical measurements, chapter 3; Bulk

density, chapter 5; and Appendix \.InJ. Uveday(ed.) Methods of analysis of irrigatedsoda. Technical Communication no. 54, Comw. Bur. Soils, Comw. Agric, Bureaux.Farnham Royal. Bucks. England,

Mintzer, S. 1961. Comparison of nudear and sud-coae methods of density and moisturedeterminations for four New York Sate soils, In Symposium on nudear methods formeasuring soil density and moisture. Am. Sot Testing Mater., Spec. Tech. Pub. 293:45-J^«

TIsdall, A. L 1951. Comparison of methods of determining apparent density of soils. AUSLJ. Agric. Rat. 1349-354,

U. S. Department of Agriculture. 1954. Diagnosis and improvement of saline and alkalisoilt. USOA Handb. 6a

Vomocil. J. A. 1954. In situ measurement of soil bulk density. Agric. Eng. 35:651-654.

ramma photons1 centimeters of

JI as designs de-'s. But it is im-<thet ditions

ana knowl-levels ac-

; A R 3 0 0 8 7 5I

Designation: 0 2216 - 80 An Arrwian *mrm St*xar«

Standard Method forLaboratory Determination of Water (Moisture) Content of Soil,Rock, and Soil-Aggregate Mixtures1

This suadvd U isued under tbc fixed destination 0 2216; the number immedivdy CoUowiof the desiinitjoo iadicitet the feu otonfmai adoption or, in ibe cue of revision, the yew of UK rrnsott. A number m ptmtbeM indicate* the y«w of la« rempprovtl. Asuperscript cpnloa (0 indicate* aa aditohal citinge uace the tat revuioa or retpproviL

1. Scop*t.l This method coven the laboratory determination of

the water (moisture) content of soil, rock, and soil-aggregatemixtures by weight For simplicity, the word "material"hereinafter refers to either soil, rock, or soil-aggregate mix-tures, whichever is most applicable.

1.2 The water content of a material is defined as the ratio,expressed as a percentage, of the mass of "pore" or "free"water in a given mass of material to the mass of the solidmaterial particles.

1.3 This method does not give true representative resultsfor materials containing significant amounts of hailoyste,montmorillonite, or gypsum minerals; highly organic soils;or, materials in which the pore water contains dissolved solids(such as salt in the case of marine deposits). For a materialof the previously mentioned types, a modified method of• *ing or data calculation may be established to give results

osistent with the purpose of the test

2. Summary of Method2.1 The practical application in determining the water

content of a material is to determine the mass of waterremoved by drying the moist material (test specimen) to aconstant mass in a drying oven controlled at 110 ± 5'C andto use this value as the mass of water in the test specimen.The mass of material remaining after oven-drying is used asthe mass of the solid particles.

3. Significant u4 Uw3.1 For many soil types, the water content is one of the

most significant index properties used in establishing a cor-relation between soil behavior and an index property.

3.2 The water contest of a soil is used in almost everyequation expressing ihc phass relationships of air, water, andsolids in a given volume of material.

3.3 In fine-grained (cohesive) soils, the consistency of agiven soil type depends on hs water content The watercontent of a soil, along with its liquid and plastic limit, isused to express its relative consistency or liquidity index

1 Tta attfc* » uate dn jurwfcao* at ASTM CMUUOM I* 1S M Sail u*Rock ud it tfct dfaw npoaUkty ofSubcommim* Ol 1.03 M Tcmn, nMnty••<d Dewy QMnamna at Soik

Cunrn tdi&M te*mmi Mty 30,19*0. Pubfch* July 19*0, Ohj^y pofeI • O 22l«-«3 T. LM prmw «MM 0 22l«-7|.

3.4 The term "water" as used in geotechnical engineeringis typically assumed to be "pore" or "free" water and notthat which is hydrated to the mineral surfaces. Therefore, thewater content of materials containing significant amounts ofhydrated water at in-situ temperatures or less than 1 10*C cube

3.5 The term "solid particles" as used in geotechnicalengineering, is typically assumed to mean naturally occurrimmineral particles that are not readily soluble in water. Ther*fore, the water content of materials containing extraneoumatter (such as cement, etc), water-soluble matter (such asalt) and highly organic matter typically require special treat-ment or a qualified definition of water content

4. AppentM4. 1 Drying Oven, thermostatically-controlled, preferably d

the forced-draft type, and maintaining a uniform temperanoiof 110 ± S*C throughout the drying chamber.

4.2 Balances, having a precision (repeatability) of ±0.01 »for specimens having a mass of 200 g or less, ±0. 1 g fspecimens having a mass of between 200 and 1000 g, or ±g for specimens having a mass greater than 1000 g.

4.3 Specimen Containers — Suitable containers madematerial resistant to corrosion and a change in mass up*repeated heating, cooling, and cleaning. Containersclose-fitting lids snail be used for testing specimens ha vim'mass of less than about 200 g; while for specimens bavins'mass greater than about 200 g, containers without lids oufbe used (Note 1). One container is needed for eachcontent determination.

Non I— Tbtpuipowofciaw-fiaiaflidiittopRvnttoHai'moiiH'uOfll 9BCU&IM HHIW tflltSU **l£"l">^ MM tO pVEVCAt UMXpOOB •tnouPin from tfat taoo&u* foUowi^ drying md bcfoct fail warins. ',

4.4 Desiccator— A. desiccator of suitable size (a conventsize is 200 to 250-mm diameter) containing a hydrous sd*geL This equipment is only recommended for use ***containers having dote-fitting lids are not used. See 7.4.1*?

5. SMfto5.1 Keep the sampks that are stored prior to testinl

nonconodibie airtight containers at a tempr: raretpproximatery 3 and 30*C and in an area uwcontact with w"''tnt.

5.2 The water content determination should be dot*

262 A R 3 0 0 8 7 6

"1 .^ as practicable after sampling, especially if potentially*0rodibie conuinen (such as steel thin-walled tubes, paint

.) or sample bags ire used.

and

ountsaf-O'Cca,

(such*ialtreav

erabryof

1.1 g forJ ,or±i

jnade of»SSers

having ilids any:h wiar

orpboarfml we*

nvenieaDussibciise who7.4.1.

"rstingiibctweBi

ntsdutfl

^ Test Specimen$.1 For water contents being determined in conjunction

jits another ASTM method, the method of specimen selec-yp specified in that method controls.

5,2 The manner in which the test specimen is selected andrequired mass is basically dependent on the purpose (ap»

tion) of the test, type of material being tested, and theof sampje (specimen from another test, bag, tube, split-i, etc.). In all cases, however, a representative portion of

total sample shall be selected. If a layered soil or moreone soil type is encountered, select an average portion

individual portions or both, and note which portion(s) wasted in the report of the results.6 J.I F°r bujk samples* select the test specimen from the

material after it has been thoroughly mixed. The mass of001st material selected shall be in accordance with the follow-ing table:ta« Rcuiaiaf, More Than About 10 % of RwommesMted Minimum Ma* of

Sunpkt MoiM Speomm, |100 to 2002.0 mm (No. 10)

4.73 mm (No. 4)19 mm31 mm76 nun

300u 500500tolOOO

1500(030005000 to 10 000

6.22 For small (jar) samples, select a representative per-ooo in accordance with the following procedure:

6.2.2.1 For cohesionless soils, thoroughly mix the material,then select a test specimen having a mass of moist materialia accordance with the table in 6.2.1. See Note 2.

6.2.22 For cohesive soils, remove about 3 mm of materialfrom the exposed periphery of the sample and slice it in half(to check if the material is layered) prior to selecting the testspecimen. If the soil is layered see 6.2. The mass of moistmaterial selected should not be less than 25 g or should be inaccordance with the table in 6.2.1 if coarse-grained particlesare noted. (Note 2).

6.3 Using a test specimen smaller than the minimum massindicated previously requires discretion, though it may beadequate for the purpose of the test. A specimen having amats less than the previously indicated value shall be notedm the report of the resatm.

Non 2—la many cam, **a» workint with a small sample oaatain-•g a relatively large ooantfiaMd particle, it is appropriate not to•dude this particle m tat Ml tatritafi If this occurs, it should beaot*4 ia the report of tkt fa-ate

T • » - - - - « . . . -• rrocenre7.1 Select representative test specimens in accordance with

Section 6.12 Place the moist specimen ia a dean, dry container of

known mass (Note 3), set the tid securely in position, anddetermine *^y 1*1*** of the coflt*i**^r ***** moist irtm^fr^^H "*»"gta appropriate balance (4.2). Record these values.

7 J Remove the lid and place the container with moist•aerial in a drying oven maintained at 110 ± 5*C and dryto i constant man (Notts 4,5, and 6X

02216Non 3—To assist in the oven-drying of larfe ten specimens, they

should be placed in containers hiving a large surface area (such as pans)and the material broken up into smaller aggregations.

NOTE 4-Tbe time required to obtain constant man will wry depend-ing on the type of material, size of specimen, oven type and capacity.and other actors. Tbe influence of these actors generally can be estab-lished by good judgment >nd experience with the materials being testedand the apparatus being used. In most cases, drying a teat specimen overnight (about 16 h) is sufficient In cues where there is doubt concerningthe adequacy of drying, drying should be continued until the mast aftertwo successive periods (greater than '/i h) of drying indicate an insignifi-cant change Oest than about 0.1 %). Specimens of sand may often bedried to constant mass in a period of about 4 h, when a forced-draft ovenis used.

Non 5—Oven-drying at 110 ± 5*C does not always result in watercontent values related to the intended use or the basic definition especiallyfor ™««*««i« containing gypsum or other minerals having significantamounts of hydrated water or for soil containing a "pi^m amount oforganic material. Ia many cases, and depending on the intended use forthese type* of mi**"*1*, it might be more applicable to maintain thedrying oven at 60 ± 5*C or use a vacuum desiccator at a vacuum ofapproximately 133 Pa (10 mm Hg) and at a temperature ranging between23 and 60*C for drying. If either of these drying methods are used, itshould be noted ia the report of the results.

Non 6—Since some dry materials may absorb moisture from moistspecimens, dried specimens should be removed before placing moistfr* "?*** ia the oven. However, this requirement a not applicable ifthe previously dried specimens will remain ia the drying oven for aaadditional time period of about 16 h.

7.4 After the material has dried to constant mass removethe container from the oven and replace the lid. Allow thematerial and container to cool to room temperature or untilthe container can be handled comfortably with bare handsand the operation of the balance will not be affected byconvection currents. Determine the mass of the containerand oven-dried material using the same balance as used in7.2. Record this value.

7.4.1 If the container does not have a lid, weigh the con-tainer and material right after their temperatures are suchthat the operation of the balance will not be affected byconvection currents or after cooling in a desiccator.

Non 7 fruiting ia a desiccator is recommended since it preventsabsorption of moisture from the atmosphere during coding.

8. CakmiatfcM8.1 Calculate the water content of the material as follows:

- Wt)i(Wt - wt)\ x 100 - •• x 100where:w water content, %,

mass of container and moist specimen, g,mass of container and oven-dried specimen, g.«n««f of container, g,mass of water, g, andmats of solid particles, g.

9.9.1 The report (data sheet) shaO include the foOowig9.1.1 Identification of the sample (material) 1

by boring number, sample number, test number, <9.1.2 Water content of the specimen to the i

or 1 %, dependinf on the purpose of the test

f lR300877

9.1.3 Indication of test specimen having a mass less thanthe minimum indicated in Section 6.

9.1.4 Indication of test specimen containing more than- soil type (layered, etc)..1.5 Indication of the method of drying if different from

oven-drying at 110 ± 5*C

02216

9.1.6 Indication of any material (size and amount) ex.eluded from the test specimen.10. PredskM and Accuracy

10.1 Requirements for the precision and accuracy of thistest method have not yet been developed.

n» Afntrtetn SocMy tor Tttttog ma MnrUft atm no octtttan rmoteang «• nttxy or* trip <wtfi *rf ttnt intnaentd m (ft* «ane*rtf. UMr* at tfttt sanotra «r» txpnuly te^ta vm Jtttmnp«M rigfn, «xJ tfw ntt * irKHngirmnr rf «UB/I ngMi. an •nOn M«r own rtteon

f»c/in<e«< eammnttf tnd mutt tit r »vy «« y««r» andnut itirxMrt it *uty*cr re r*yMbr> « anx *"• Oy m* /rf net runted, t*t*r fttpomtd or wtMmm. four eemmtnt tn latiM *U*r for nrttteii of tf* tnndifO or tor laauontl si!***mi thouH 0» taarttna » ASTV iiMdpuirtin. Xour eorriffuna w* rvcttim evMU oomiMrHtan « • trmtnnj o/ (fw fMpon»Mtttchnc* uJ»t»niM» wftieA you nwy «t»nrj. Ityculttttfm your ojrnn»m /MM not rtert«tf • Mr ANring you jrtouB nwk» yourvww»tox3wnforf>»ASTWCor7VT)iB»»onSf«W*rtt. 1918 tot St., PHtoOtlphtf. M 19103.

264f lR3-00878

Attachment 6

1. Sieves must be calibrated/checked according to Attachment 3from "Procedures in Sedimentary Petrology", as detailed onpages 65-67. Sieves must be calibrated with standard samplesor measurement of openings and must meet specifications ofTable l. Narrative must describe procedure and data packagemust contain sieve accuracy testing results.

2. Samples must be prepared for analysis by ASTM D-421(Attachment 2).

3. Grain size analysis by ASTM D-422 (Attachment 1). Analysismust follow ASTM D-422 and must employ both sieve andhydrometer analysis as specified.

4. Percent moisture must be determined as per Section 8 of themethod.

5. Report requirements and data specifications are detailed inSection 18 of the method.

6. Laboratory must comply with purge file requirements.Contact SMO for details.

SR3QQ879,

Attachment 7

Data package must include: all raw data, all instrument and/orequipment calibration results, calculations, blank results,duplicate results, chain-of-custody forms, SAS request forms, SASpacking list(s), or traffic report(s), copy of airbill(s)confirming sample receipt, and copies of analyst's logbooks (signedby analyst) with date and time of sample preparation and analysis.

The cover page and all sample reports forms MUST be labeled withthe complete EPA sample number as it appears on chain-of-custodyand CLP paperwork.

The case narrative must document all problems encountered and thesubsequent resolutions. List instrumentation and methods employedfor analysis.

For grain size distribution, the deliverables required in ASTMD422-63, Section 18 must be included. Also, include NBS Class "S"weight specifications for accuracy. Include balance check resultsof the actual balance reading for each weight used. Plots ofparticle size raw data must be included in the data package.

Graphical report of Grain Size must be done as per Section 18.12 ofmethod.

Results of balance check must be reported.





B. RSCC Representative; COLLEEN WALLINGC. Telephone Number; (301) 266-9180

p. Date of Request:____________


Please provide below description of your request for SpecialAnalytical Services under the Contract Laboratory Program. inorder to most efficiently obtain laboratory capability for yourrequest/ please address the following considerations, ifapplicable. Incomplete information may result in a delay in theprocessing of your request. Please continue response on additionalsheets, or attach supplementary information as needed.

l. General Oescrition of analytical services requested:

Extraction of 6 soil samples by a modification of the TCLPExtraction method with the extracts being analyzed for TCLorganics by the 3/90 CLP Organic SOW and for TAL metals by the3/90 CLP Inorganic SOW.


6 low/medium concentration soil samples and 2 rinsate blanksto be subjected to a modification of the TCLP extractionprocedure and the extracts analyzed for TCL organics and TALmetals.


RI/FS - ARCS III


• f lR30088 !


To be determined.


To be determined.





TCLP Extraction - Appendix II of 40 CFR 261 except that onlyreagent water is to be used 'as the extraction fluid.

Analysis - TCL compounds by the 3/90 CLP Organic andInorganic SOWs.


8. Special technical instructions (if outside protocolrequirements, specify compound names, GAS numbers, detectionlimits, etc.):TCLP extraction must be indicated on all Form I's.Only reagent water is to be used as the extraction fluid.

9. Analytical results required (if known, specify format for datasheets, QA/QC reports, Chain-of-Custody documentation, etc.)*If not completed, format of results will be left to programdiscretion:

All raw data. Deliverables as per the CLP SOWs. In addition,copies of TCLP extraction log book, signed and dated copy ofchain-of-custody documentation, copies of air bill confirmingsample receipt, and SAS Request Form are also required.

10. other (use additional sheets or attach supplementaryinformation, as needed):




AR30G882


Parameter__________Detection Limit_____(+/-% or Concentration)

All compounds As per CLP SOWs As per CLP SOWs



All compounds As per CLP SOWs As per CLP SOWs


As per CLP SOWs.


Gregory L. Zimmerman - NUS Corporation - (412) 788-1080,June 6, 1991.



AR3QQ883







D. Date of Request:______________




Analysis of 42 aqueous and non-aqueous drum, tank, and pipingsamples for TCL Organics by the 1/88 Multi-Media; High/MediumConcentration SOW.


42 unknown concentration aqueous and non-aqueous drum, tank,and piping samples for TCL Organics by the 1/88 Organic CLPSOW. Concentrations are expected to be below 30 ppm.


RI/FS - ARCS III



To be determined.


To be determined.

Samples will be shipped overnight by overnight aircarrier. This schedule is tentative and is dependant onthe project remaining on schedule. Sampling may continueinto the week of


35 days from receipt of last sample.


Analysis of TCL Organics by the 1/88 Revision of "Statement ofWork for Organic Analysis; Multi-Media; High/MediumConcentration".


If. more than one phase is present, all phases must beanalyzed separately. Sample must be screened prior toanalysis and if level of contamination is shown to beless than 20,000 ug/1, contact SMO immediately forfurther instructions.


As per the CLP SOW.




Jeff Orient - NUS Corporation(412J-788-1080.

flR300885


Parameter__________Detection Limit______( + /-% or Concentration)

TCL Organics (non-aqueous) 1 ppm As per the CLP SOW

TCL Organics (aqueous) 30 ppb As per the CLP SOW



As per the C-LP SOW.

14. Action Required if Limits are"Exceeded:

As per the CLP SOW.


Gregory L. Zimmerman - NUS Corporation - (412) 788-1080June 6, 1991, revised September 5, 1991.



flR300886




A. EPA Region/Client;EPA-REGIQN IIT-ARCS ill


C. Telephone Number; (301) 266-9180D. Date of Request:____________E. Site Name; AIW FRANK, CHESTER COUNTY, PA

Please provide below description of your request for SpecialAnalytical Services under the Contract Laboratory Program. Inorder to most efficiently obtain laboratory capability for yourrequest, please address the following considerations, ifapplicable. Incomplete information may result in a delay in theprocessing of your request. Please continue response on additionalsheets, or attach supplementary information as needed.1. General Descrition of analytical services requested:

Analysis of 42 aqueous and non-aqueous drum, tank, and pipingsamples for TAL metals by the 7/87 High ConcentrationInorganic CLP SOW. Samples may be oil, solid or liquid andmay be in several phases. CN~ and S~* must be analyzed byMethod 376.62 and not by the spot test.


42 unknown concentration aqueous and non-aqueous drum, tank,and piping samples for TAL metals by the 7/87 HighConcentration Inorganic CLP SOW. Concentrations are expectedto be below 30 ppm.

3. Purpose of analysis (specify whether Superfund(enforcement or remedial action), RCRA, NPDES, etc.):RI/FS - ARCS III


QR300887


To be determined.


To be determined.


i




Analysis of TAL metals by "Statement of Work for InorganicAnalysis; Multi-Media; Multi-Concentration1, 7/87 Revision.CN~ and S~2 must be analyzed'by Method 376.62 and not by thespot test.

s. Special technical instructions (if outside protocolrequirements/ specify compound names, CAS numbers/ detectionlimits/ etc.):

If samples are multi-phase, analysis of each phase isrequired. If samples are determined to be at lowconcentration levels, contact SMO immediately for furtherinstructions.

9. Analytical results required (if known/ specify format for datasheets/ QA/QC reports, Chain-of-Custody documentation/ etc.)*If not completed, format of results will be left to programdiscretion:

As per the CLP SOW.

10. Other (use additional sheets or attach supplementaryinformation/ as needed):




AR300888

12. Data Requirements:

Parameter________Detection LimitPrecision Desired

(+/-% or Concentration)

TAL Metals (non-aqueous) 1 ppm

TAL Metals As per the 7/87 CLP SOW(aqueous)

As per the 7/87 CLP SOW

As per the 7/87 CLP SOW



As per the 7/87 CLP SOW.


As per the CLP SOW.


Gregory L. Zimmerman - NUS Corporation - (412) 788-1080,June 6, 1991.


Please return this request to the sample Management Office as soonas possible to expedite processing of your request for SpecialAnalytical Services. Should you have any questions or need anyassistance/ please contact your local Regional representative atthe Sample Management office.

AR300889

ftlu */(*U.S. ENVIRONMENTAL PROTECTION AGENCY SAS NUMBERCLP SAMPLE MANAGEMENT OFFICEP.O. BOX 818 - ALEXANDRIA, VIRGINIA 22313PHONE: 703/557-2490 - FTS/557-2490



A. EPA Region/client ;EPA-REGION in-ARCS inB. RSCC Representative; COLLEEN WALLING

C. Telephone Number: (301) 266-9180


E. Site Name: AIW FRANK, CHESTER COUNTY. PA

Please provide below description of your request for SpecialAnalytical Services under the Contract Laboratory Program. Inorder to most efficiently obtain laboratory capability for yourrequest, please address the following considerations/ ifapplicable. Incomplete information may result in a delay in theprocessing of your request. Please continue response on additionalsheets, or attach supplementary information as needed.


Extraction of 40 aqueous and non-aqueous drum, tank, andpiping samples by the TCLP Extraction method with the extractsbeing analyzed for the TCLP Metals by the 3/90 CLP InorganicSOW. See Attachment 1 for the full list of TCLP metals .


40 unknown concentration aqueous and non-aqueous tank, drum,and piping samples to be subjected to the TCLP extractionprocedure and the extracts analyzed for TCLP metals. SeeAttachment 1 for the full list of TCLP metals.


RI/FS - ARCS III


HR30089Q


To be determined.


To be determined.






TCLP Metals Analysis - 3/90 CLP Inorganic SOW

TCLP results are to be reported in ug/L.



All raw data. Deliverables as per the CLP SOWs. In addition,copies of TCLP extraction log book, signed and dated copy ofchain-of-custody documentation, copies of air bill confirmingsample receipt, and SAS Request Form are also required. TCLPextraction must be indicated on the Form I's.


Laboratory must comply with CSF requirements as specifiedin the 3/90 SOW. Laboratory will be responsible for thedisposal of all sample remnants and extracts.



flR300891







With the following deviation:

Spike one TCLP leachate with_ all of the TCLP regulatedmetals. Provide all recovery data but do not performrecovery corrections.




Gregory L. Zimmerman - NUS Corporation - (412) 788-1080June 6, 1991, revised September 5, 1991.



aR300892

/f I ( ' - - - - - - — (

Federal Register / Vol. 55. No. 61 / Thursday. March 29. 1990 / Rules and Regulations

calculated regulatory level (i.e., thechronic toxicity reference levelmultiplied by the DAF) i* below theanalytical quantitation limit, the

quantitation limit is the final regulator}'level. Note that the list of constituents inTable IL2 contains trie 14 constituentscurrently regulated under the existing

EPTC. As specified in today's rule, theseconstituents will continue to beregulated at their current levels.

TABLE 11.2.—TOXICTTY CHARACTERISTIC CONSTITUENTS AND REGULATORY LEVELS———————— — —

EPAHWNo.1

D00<DO05DOHO0060019D0?0D0?1D0220007D0230024D02SD026D016D027CX32BD029D03000:2D031D032D033D034D008O013O009O014O035DOSSD037D03SD010D011

0015 • ".D04CDM1 . . -:XX2 -D017XK3

Constituent (mg/L)

SVatrffl in i • -•- - - - - -Benzene ————————————————— . ————————————— — ..

C*^wofrffl\r§ne i . T-.n-r-

m-Cf«v>) 3 0i£iJihMi ......tC.JLSfL.?.., ......... . , . , . , _,......„... ___ .....

Csesol2 «.0 . ... _ . _1 4-D*cti'(yptH>n7*n^ .. .. .. . , ..... . . . . . . . .. ...1.2-QshIoroelhane _._.,.._............._.......... „._.._.„.........„ ......... _ ......1 1-DiChlofw»thy*enfl. . ... _ ._........,......... . ... ........Z 4-DtnitrolOluftnff - .. ......... ., ..... _ ...............Enflfn. . . ........ .......... ....... _ .._. ... . . . ™. . , ...... ...... ,_.Mapnchinr («nrl rt« hyrtfnnrt*! . . . . . . . _ . _ . . _ . . _ . . _ . _ . . _ . . _ .

Heucnioro-1,3-buiadiene.. __ .-• — -- - _ ..__.._. _ ..... ____ . _ ._...

Lead «. . . , , -•- -- -|j»wf(n^

M»t'xn'yeh'of — - - • -Mfitftyl ttrtyt ktlon*.... ........ __, . . _..._.... ... .._...Nitrofrflnzerys ... . ,A . - ,.,..,_,.,.,,.,....

Pyndine .. ' , . , , , .

Silver

Tnehlnrpamylan. , ,_.. .,. . . . . . . . . . . . . . . ._. . .... .....^. ...... ......?>,*-Tnrrt<vr>pl\»nnl r ,. . . ., .2,4,&-Tnctitoropheno! _ _________ .. __ ,. ____ '„ __ . _ __.._ __ ...?,4,5-T {$-l"«v) ..._.,..„...„.„., . . . . . .Vrryt ehi™'c)t........ ... , ......,.,„,. ..„

CAS No1

74XO-38-?7440-39-3

71-43-27440-43-9

56-23-557-74-9

100-90-767-66-3

7440-47-39S-4S-7

10S-3S-410&-44-5

94-75-7106-46-7107-06-275-35-«

121-14-272-20-876-44-8

110-74-167-66-367-72-1

7439-&2-156-89-9

7439-97-C72-S3-S76-83-398-95-387-86-5

110-66-T7782-49 27440-22-4

127-18-48001-35-2

79-01-685-95-485-06-293-72-175-01-4

(•v*(m0/L)

0,051.00.0050010.0050000310.060.052222010.0750.0050.0070.00050.00020000080.00020.005C.030.050.0040.0020.120.0210.040.010.050.0370.0050.00540.020.010.002

teve' (mj'L)

501000

051.005003

1000605.0

• jnc o ••2000 ••2000 f4 200 0 •

100750,50,7

'0.130020008

•0,130,53.05.00.4C A

10,02000

20*10CO •

*S,0 *\ 05,00,7

' 0,50.5

400,0*2.0 .1.00,2

wesie number.* Ctomicil iDsiracl; service numb«'.* Ouanbiabon hmil is g'eaiar man tne calculated regda'.txy (eve!. The auantutian linvt therefore becomes the reputat:xy level.4 ff 0-, nv. tntf p-cresol concentratians eanno: ix> drtteranuated, the tau.' cressl (D02S) conconfajan is useC. The rej-Jaicwy level lor lotii creso! is 200 mg/l.

The regulatory- levels reflectindifications to some chronic toxicityjference levels since the originalroposai. EPA has revised some of thefaxuxmm Contaminant Levels, Risk-pecific Doses, and Reference Doses to•fled new data and better methods. Insponse to comments received, EPAis decided not to apportion reference>ses of noncarcinogens to account forultiple routes of exposure, as wasiginalJy proposed (51 FR 21648). Seectioa ULC for further discussion ofmmeaU on apportionment and the,'ency's reasons for not includingportionment of reference doses in theal rule. Today's rule also promulgatesTCLP to replace the EP. The TCLP

>resents an improvement over the EPhat it more accurately addresses

leaching potential for use in evaluatingwastes containing organic constituents,and also corrects several minortechnical deficiencies in the original EP.The version of the TCLP promulgatedtoday reflects additional improvementsand modifications made to the TCLPsince the original proposal The TCLPpromulgated today will also replace theearlier version of ths TCLP promulgatedas part of the land disposal restrictionsprogram.

Today's rule incorporates a schedulefor compliance that classifies theuniverse of potentially affected TCwaste handlers into two groups: fl) Allgenerators of greater than aOO kg/monthand less than 1,000 kg/month ofhazardous waste (small-quantitygenerators) must come into compliance

with the subtitle C requirements formanagement of their TC waste within 1yean and (2) all generators of 1.000 kg/month or more of hazardous waste arerequired to comply with all subtitle Crequirements for TC wastes within 6months. The phased schedule forcompliance is further discussed insection V. . '.

Wastes identified as hazardous underthe Toxicity Characteristic will alsobecome hazardous substances undersection 101(14) of the ComprehensiveEnvironmental Response,Compensation, and Liability Act of i960(CERCLA), as amended. Today's ruleamends the list of reportable quantities(RQs) in 40 CFR part 302 by addingappropriate values for each of the new25 TC toxicants. All of the newly-

QR300893







D. Date of Request:_____________

E. Site Name: AIW FRANK. CHESTER COUNTY, PA



Extraction of 40 aqueous and non-aqueous drum, tank, andpiping samples by the TCLP Extraction method with the extractsbeing analyzed for the organic TCLP Parameters by the 3/90 CLPOrganic SOW and SW-846, Method 8150. Add pyridine and 3methylphenol to the semivolatile method target list. SeeAttachment 2 for the full TCLP constituent list.


40 unknown concentration aqueous and non-aqueous drum, tank,and piping samples to be subjected to the TCLP extractionprocedure and the extracts analyzed for the organic TCLPparameters. Analyze VOAs, BNAs, and Pesticides by the 3/90CLP SOW and the herbicides by SW 846, .Method 8150.


RI/FS - ARCS III


f t R 3 0 0 8 9 i *


To be determined.


To be determined.



Completed data packages are due within 35 days from receipt oflast sample..



TCLP Organic Parameters Analysis (VOAs, BNAs, Pesticides)by the 3/90 CLP Organic SOW,

TCLP Herbicide Analysis by SW 846, Method 8150.




All raw data. Deliverables as per the CLP SOWS. In addition,copies of TCLP extraction log book, signed and dated copy ofchain-of-custody documentation, copies of air bill confirmingsample receipt, and SAS Request Form are also required. TCLPextraction must be indicated on all Form I's.


Laboratory must comply with the CSF requirements asspecified in the 3/90 SOW. Laboratory will beresponsible for the disposal of all sample remnants andextracts.


Jeff Orient - NUS Corporation(412J-788-1080.

HR300895


Parameter_________Detection Limit_____(+/-% or Concentration)





See Attachment 1 for additional requirements.




Gregory L. Zimmerman - NUS Corporation - (412) 788-1080June 6, 1991; revised September 5, 1991.



SR30G896

ATTACHMENT 1

13. QC Requirements: For TCLP Organics by OLM01.0 (3/90), followQC requirements specified in the SOW with the following deviations.

13. A. All TCLP target compounds must be spiked. Report allrecoveries but do not perform recovery correction. Chlordane andToxaphene will require separate leachate aliquots for the matrixspike because of their multicomponent responses. Generation ofsufficient leachate volume for spiking may require the lab to spikeleachate aliquots from more than one sample. Matrix spikeduplicates are not required except for herbicides if volume allowsas stated below.

13. B. Pyridine and 3-Methylphenol must be added to thesemivolatile analysis. Achieve the following criteria for Pyridineand 3-Methylphenol:* Calibrate at 5 levels.* Minimum relative response factor » 0.010* Quantitate using the internal standard with the closest retentiontime (must be free of interferences) to the Pyridine and 3-Methylphenol peaks individually.* Quantitate using the most abundant m/z that is free ofinterferences. Major ions for Pyridine are 79, 52, 51 and 50(descending abundance) . Major ions for 3-Methylphenol are 107, 108,77, 79, 90. If coelution occurs among some or all of theMethylphenol isomers, the quantitation method and the final report(Form Is) must reflect the sum of the isomers (e.g., Total 2 and3-Methylphenol or Total Cresol).

13.C. For analysis of 2,4-D, 2,4,5-T, 2,4,6-T and Silvex, followQC specified in SW 846 method 8150.* Perform a matrix spike (60-120% recovery) and, if volume allows,a matrix spike duplicate (<30 RPD).* Perform a sample duplicate (<30 RPD).* Perform a method blank (<MDL for all target compounds).* If greater than %50 separation cannot be achieved for 2,4,5-T and2,4,6-T, quantitate and report as total Trichlorophenol.

AR30Q897

2-118O4 Federal Register / Vol. 55. No. 61 / Thursday. March 29, 1990 / Rules and Regulations

calculated regulatory level (i.e.. thechronic toxicity reference levelmultiplied by the DAF) is below the

.lytical quantitation limit the

quantitation limit !• the final regulatorylevel. Note that the list of constituent* inTable 0.2 contains the 14 constituent!currently regulated under the existing

EPTC Ai specified in today'* rule, theseconstituents will continue to beregulated at their current levels.

TABLE 11.2.—TOXICTTY CHARACTERISTIC CONSTITUENTS AND REGULATORY LEVELS

EPA HW No '

D0040005t»18O006D01SD0?00021D022DO073023DOJ4X253026»16 ,X27»28X29XJ3CX12503 T»22W33«3<008013O09014035036

•J3T315 • 'UOU/! . . -

-J«2U7*3

Concttutflt (mg/L)

Ar*»~r

tenum. _. _,_,._. ..,.., ..., ...........•y>ru>n» ———————————————————————————

*J-.,**r,\ t. ^,+Wfl^V^I~*Am~J S .««LTI^^, lfl« »..«(

pJf.»fnJ H «*r,*tl»1rf-n-- 1r/tfrt ,i • -1 t-pifhiyrft^ntfnt , ,.,,,,.„.„..,.,...,„......,.,..,, .... — ,.- ..- .„,-._„, .,1,?.Ckchlon>fthl"f ,,....,....„,,,,..._,...,,......,..,,,,, , . , . , . „_, ., , ,. ,,l1i-ftehioro»iRy1ff ......... ............... ,_„...,„_...,„.,• ......... ................

Erw*""...,...,,,—.™......,.-. ........ ,,Wfptjrhlnr (fnri ^ Syflrprrfl.) , ,.,..„.__, ._.,.,HaorMnmhannn*

l.tl'J , , ., ,, ... , . . . _... .L«rt»rn.

u^thorycWQ' ,___. — .,

Pfnla.fWnrciphnnnl...,, ..„.,„.„.,.,

StleT/lP" ...I ... I-MIMI I ————

£j)y0r _ ^_ M . i i i i • i i

24,5-Tnchiomnhenoi .... _,.,_. . , „ ..,, „ ..

?.4,s.TP (s:h»X) ,.. . .... ,,..,,,,,...,..,. ,.,Vinyl rhionrt. ,.., ,„,_,, ,..„..,.,.„

CASNo.'.

7*X 0-38-27440-39-3

71^3-27440-43-8

56-23-567-74-9

106-90-767-66-3

7440-47-3B5-46-7

10S-3S-4106-44-5

84-7S-71 OS-46-7107-06-275-35-t

121-14-272-20-876-44-6

110-74-1B7-6S-367-72-1

743»-»2-1S0-89-9

7439-97-C72-43-576-63-396-95-387-86-5

110-66-17782-49 27440-22—*127-16-4

8001-35-279-01-605~«S-4M-06-283-72-175-01-4

Ovane tobctty nttttnetto^frnBCU

0.051.00.0050.010.0050.000310.060.0522i20.10.0750.0050.007C.00050.03020.000080.00320.005ft n«j

b.CS0.0040.0020.120.0210040.010.050.0070.005O.OC54O.C20.01

• 0.002

•rce! (mj'L)

50103.0

O.S1.00.50.03

100.0e o5.0

• 200 0 ••2000 •4 2OO.O •' 200.0 •

10.07.5050.7

•0.130.020,008

•0 130.53.05.0040.2

10.020CO"

2,0*100.0 •«5.0 *

; i)5.00.7

' 0.505

400.0*2.0 •1.0OS

1 Hii|-tJ>--s »£ile number.* Ctwni=i! abstract: service numbe'. '• Ouanuiabon Nmit ts g^eaiar tn»n ne c»lsui«ted r«jj1atofy to»el. The outnftaDori Sn* mer«lor» b*co!nes th* repdiuxy level.4 (t o-, nv, and p-eresoJ concentrations anno: s* tJrt)»r«nuai«d. me tout erase! (OC25) concanfa'uan » usaeL Tr« reg-Jatory tov»! for tout crcso! is 200 mg/l.

The regulatory levels reflect)dificaUons to some chronic loxicity'erence levels since tie originalsposai. EPA has revised some of theiximum Contaminant Levels, RJsk-°cific Doses, and Reference Doses tolect new data and better methods.. Inponse to comments received. EPA> decided not to apportion referenceits of noncarciaogens to account forItiple routes of exposure, as wasfinally proposed (51 FR 21648). Seetioa IILC for further discussion of

^.imenU.on apportionment and themcys reasons for not includingortionment of reference doses in the.Ijyle. Today's rule also promulgates

"' to replace the EP. The TCLPIts an improvement over the EP: more accurately addresses

leaching potential for use in evaluatingwastes containing organic constituents,and also corrects several minortechnical deficiencies in the original EP.The version of the TCLP promulgatedtoday reflects additional improvementsand modifications made to the TCLP$incc the original proposal The TCLPpromulgated today will also replace theearlier version of the TCLP promulgatedas part of the land disposal restrictionsprogram.

Today's rule incorporates a schedulefor compliance that classifies theuniverse of potentially affected TCwaste handlers into two groups: [1] Allgenerators of greater than 100 kg/monthand less than 1,000 kg/month ofhazardous waste (small-quantitygenerators) must come into compliance

with the subtitle C requirements formanagement of their TC waste within 1yean and (2) all generators of 1,000 kg/month or more of hazardous waste arerequired to comply with all subtitle Crequirements for TC wastes within 6months. The phased schedule forcompliance is further discussed insection V.

Wastes identified as hazardous underthe Toxicity Characteristic will alsobecome hazardous substances undersection 101(14] of the ComprehensiveEnvironmental Response,Compensation, and Liability Act of 1980(CERCLA). as amended. Today's ruleamends the list of reportabie quantities(RQs) in 40 CFR part 302 by addingappropriate values for each of the new25 TC toxicants. Al! of the newlv-

f t R 3 0 0 8 9 8



.Regional Transmittal Telephone Request

A. EPA Region/Client;EPA-REGION III-ARC8 ill







Analysis of 40 aqueous and non-aqueous drum, tank, and pipingsamples for BTU content, ash content, chlorine content,ignitability, reactivity, and corrosivity by the methodslisted in Section 7. The samples may be oil, solid or liquidand may be in several phases.


40 unknown concentration aqueous and non-aqueous drum, tank,and piping samples for the above analyses. Concentrations oforganics and of inorganics are expected to be below 30 ppm.

3. Purpose of analysis (specify whether Superfund(enforcement or remedial action), RCRA, NPDES, etc.):

RI/FS - ARCS III


HR300899


To be determined.


To be determined.





BTU content - ASTM D3286-85

Ash content - ASTM D2974-84

Chlorine content (non-aqueous) - ASTM D 808-81(aqueous) - SW 846-9020

Ignitability (non-aqueous only) - SW 846, Method 1010

Reactivity - SW 846, Section 7.3

Corrosivity (aqueous samples only) - SW 846, Method 1110

All methods are attached.


If samples are multi-phase, analysis of each phase isrequired. Calibrate balances using NBS class "S" orequivalent weights.

9. Analytical results required (if known, specify format for datasheets, QA/QC reports, chaia-of-Custody documentation, etc.)'If not completed, format of results will be left to programdiscretion:

Data sheets, signed and dated chain-of-custody forms, SASpacking list, SAS request form, copies of air billsconfirming sample receipt, and calculations. The coverpage and all sample report forms must be labelled withthe SAS and Task Number as they appear on the Chain ofCustody forms.

AR3009QO

Report balance calibration and muffle furnacetemperature. Report copies of all logbooks used duringequipment standardization. Include true values of all QCreferences.

10. Other (use additional sheets or attach supplementaryinformation/ as needed):

Laboratory must comply with purge file reguirements.Contact SMO for details.

11. Name of sampling/handling contact:Jeff Orient - NUS Corporation(412)-788-1080.

aR30090l


Parameter________Detection Limit_____(+/~% or Concentration)

Reactivity - see Attachment 1

All other parameters - per attached methods



BTU content - standardize the calorimeter per Section 10 and 11 ofASTM D3286.

Balance calibration using NBS class "S" or equivalent weights.

Laboratory Duplicate 1/10 samples < 30%(BTU, Ash, Chlorine Content)

Laboratory Duplicate 1/10 samples + 4° F(Ignitability)

Laboratory Duplicate 1/10 samples < 10%(Corrosion)

Chlorine Content Lab Blank 1/10 samples < 0.03% Section 8.6

Standardize the Pensky Marten Flash Tester per ASTM E134-68

Ignitability Reference Material 1/10 Samples + 4° AF

See Attachment 1 for Reactivity QC requiremetns


Contact Region III through the SMD (Monica McNeal, 703-519-1467).


Gregory L. Zimmerman - NUS Corporation - (412) 788-1080.June 6, 1991, revised September 5, 1991.



AR300902

(\TTf\CHHgAJf I

2.

ParameterIReactive CyanideReactive Sulfide

Detection Limit

0.10 ag/kg10 sig/kg

Precision Desired(* or Concentration)

t 20%* 20%

QC Requirement!

Audits Required

Reagent Blank

Matrix Spike- Cyanide- Sulfide

Midpoint check standard -must be distilled (Cyanideonly)

Lab Duplicate

QCrcheck standard (Sulfideonly)

Frequency of Audits

1 per batch

1/20 samples1/20 samples

1 per batch or•very 15 samples,whichever is storefrequent

1/20

1/15

t or Concentration)

Below Method DetectionLimit

£ Recovery S150Recovery S120

1 20%

* 20%

CX

f lR300903

°

D3286-85

<: COPYRIGHT by American Society forTesting and Materials.

This copy is made with the permission of A!Any further reproduction is prohibited.

I # .'f 362 d3ld003131 XO-

D*»lgnitiwv 0 3286 - 85

Standard Teat Method forGROSS CALORIFIC VALUE OF COAL AND COKE BY THEISOTHERMAL-JACKET BOMB CALORIMETER1

vnj<r ihc (*n«J 4«»i|rt«ium O }?X&. th* numbrr immtdiitd} falUminf the Joi|njnun in..n(!iii.il *iu|Muinor. Hi itw i:;ueof revision. Ihf \«ir udajl rr»ivion, A numftfr in p*t«nl(ift*t tmiMitt ihr >«M^ sutxrscnjM cpulyn M imjivjio in niunn»l vh»nf» since th« lul fcvmon or r

ihc >f if of

1. Scop*i. t This lest method cover* the determination

of the gross calonfic value of coul and coke bym<» isothermal-jacket bomb calorimeter.

1.2 The values stated in SI units arc 10 beregarded as the standard,

I ,.i 7'/i/i •nundartt »«iy involve hixurdous ma-wriali. operations, and «/w/vmw. Thin tiamiurdrfw.v mil purport to udtircsx ail of the safety proti'Icm.t axaviated with in list. It is the responsibil-ity of n-Awv«'r axes this standard to consult andfiHiblifh apprvprniiv mfi'ty and htatth practicesand </(U'rminf the uppllfabttlty ofrfxulaiory limi-tiHiun* prior ID ««•. Specific precautionary state-mvnts are given in Section 9,2. Applicable Docunwm*

2.1 M57'A/ Standard*:D121 Dcfininons of Terms Relating to Coal

and Coke1

P 346 Method of Collection and Preparationof Coke Sample* for Laboratory Analysis2

D 1193 Specification for R«ag«nt Water1

0 2013 Method of Preparing Coal Samples forAnalysis'

D .1173 Test Method for Moisture in I he Anal*>&i* Sample of Coal and Coke'

[).U77 T«t Methods for Total Sulfur in theAnalysis Sample of Coul and Coke;

011 HO Method lor Calculation C"oa' an(J C"kcAnalyses from AvDvtcrminvd to DifferentBases'

t)42.V» Tost MeilnxJ for Sulfur in the AnalysisSiimplc of C'val and C\»k« Using Highfvnipvraturc Tube Purnatc CombuMionMethods-1

I: I Sixvillcaiion for A.STM ThcrrnirnK'ter-i'l:. N4 Rtfi'Dinnivtitled Prai'tU'V lor Suk- U'w of

C)x>jcn Combusiion Bombs'

3, Terminology3.1 Definitions:3,1.1 wlortjk value— the heat produced by

combustion of a unit quantity of a substanceunder specified conditions. It is expressed in thislest method in British thermal units per pound(Btu/lb), Calorific value may also he expressedin calories per gram (cal/g) or in the InternationalSystem of Units (SI), joules per gram (J/g). whenrequired. The unit equivalents are given in Table

3,1.2 gross caloriftt value (x'ots hvat of cam-<il constant volume), Q, (grossl—xt Def-

initions D 121.3.I..1 wi ailortfc value (net heat of ctmihus-

linn at ciuwatu pressure). Qf fntt)—se« Defini-tions D 121.

3, 1 A cahirinwvr—to used in ihii test method:consists of the bomb and its contents, the calo-rimeter vessel (bucket) with stirrer. the wuter tnwhich the bomb is immersed, and the portionsof the thermometer and the ignition leads ui thini he calorimeter vessel.

3.2 Dewrtptiiin* iif Tenn\ S/H'titit In i/in

3.2. t iwrnieii t<>t»peratnn> /•/,«•— the temper-ature of the culorimeier caused by the processthat occurs inside the bomb*, that is the observedtemperature change corrected for various effectsas noted in 10.4.1.

' 7 h i > trMiiii-r tM .m ( i

iilvi>iiiniiitt\ I( uncnl nlii

vx< ()ri|inall\) \ > » 6 . I 4

' \nnuul /k«J,' \nnuul H.-4 ,' Immil /(.«<! ,' Innuul «.«4

is utxlv il < \il>v «ml \\ llw .

«l \M M ( ,n».cv\r<Misihilii> »i

Mi» .M.t j>i |n

M«nJ,nJ\. V«l II HIIXIM \t«H,l,»,i*. V,,| U III(M\l Shtn,ltt>il\ S,.l Mil.'

; " <• seieosi .'Hd 93:f t R 3 0 0 9 0 5

-6 -9 363

NOTI I —Temperature it measured in cither degreesCelHvis or dcjrecs Fahrenheit Thermometer correc-lions should be applied. Temperatures may be recordedin ohim or other arbitrary units instead of degrees.Consistent units must be used in standardization andihe actual calorific vjluf determination If arbitrary.mi< other ihan UL IVO £ iflwus or Fahrenheit are UV.M.>.?•<? ivnperafjri; interval over which all iciU arc nudenr-st not >ar> so much (hat 31 error greater than0 ixii 'C' *o«id he caused.

3.^.2 energy equivalent, heat capacity, or wa>ler equivalent—'{tit energy required to raise thetemperature of the calorimeter one arbitnry unit.This is the quantity lhat. when multiplied by thecorrected temperature rise, iben adjusted for ex-traneous heat effects, and divided by the mass ofin* simple, gives the gross calorific value.

Nun 2—Energy urms for quantities lined through-oui this lest method arc such that the number of energyunits per gram of sample corresponds exactly to thenumber of Btu's per pound of sample. For brevity theseare referred to as fllu's. The actual energies are smallerthan those stated b> the ratio of the number of poundsper gram (I/4JJ.J9), The eneri> equivalent of thecalorimeter has the units (Btu/lbl times !|/dcf>. Can.version to wrier units is discussed in Append!* Xi.Time is expressed in minutes. Mast is expressed infrtms.4. Summary of Method

4 I Calorific value in determined in ihis testmethod by burning t weighed sample, in oxygen.in a calibrated isothermal-jacket bomb calorim-eter under controlled condition?, The calorimeteris standardised by burning ben/oic acid. Thecalonlk value of the sample is computed fromtemperature observations made before, dunng,and after combustion, and making proper allow,ances for heat contributed by other processes,and for thermometer and thcrmochemical cor-rections.

NOTE .1—Oxidation after sampling of susceptiblelow-rank coal or lignite miy result in i reduction ofcalorific value. Unnecessary exposure of the sample toair from the time of sampling or delay in iniiysis shallbe avoided.$. Significance antf UM

5.1 The grow calorific value is used to com-putc the total calorific content of the quantity ofcaul reprexntcd by the sample for payment pur-poses, provided the buyer and the seller mutuallyagree upon this,

5.2 The gross calorific value is used in com-puting the calorific value versus sulfur content todetermine if the coal meets the regulatory re-quirements for industrial fuels.

J,3 The gro» calorific value may be used for

D32M

evaluating the effectiveness of bencficiation proc-esses, or for research purposes.6, Apparatus and FacHftte

6.1 rc.ii S/wu—-A room or area free fromdrafts and that can be kept at a reasonably uni-form temperature for the time required for thedetermination, The apparatus shall be shieldedfrom direct sunlight and radiation from otherheat sources. Thermostitic control of room tern*peraturt and controlled relative humidity aredesirable.

6.2 Combustion Bomb, shall be constructedof materials that are not affected by the combus-tion process or products sufficiently to introducemeasurable heal input of alteration of end prod-ucts. Tne bomb must be designed so that allliquid combustion products can be completelyrecovered by washing the inner surfaces. Theremust be no gas leakage during a test. The bombmust .be capable of withstanding a hydrostaticpressure test of 20 MPi (3000 psig) at roomtemperature without stressing any part beyondits elastic limit.

6.3 fitf/tfflff—A Irborutory balance having thecapability to weigh tht sample to the nearest0,0001 g. The balance should be cheeked period-ically to determine its accuracy.

6.4 Calorimeter Vessel, r ade of metal with atarnish-resistant coaling, .s.id »i;n all outer sur-faces highly polished. Its ;« -nail be such thatthe bomb will be completely immersed in waterwhen Ihe calorimeter is assembled. It shall havea device for stirring the water thoroughly and ata uniform rate but with minimum heat input.Continuous stirring for 10 min shall not raise thecalorimeter temperature more than 0.0IT(0.02'F) starting with identical temperatures inthe calorimeter, room, and jacket. The immersedportion of the stirrer shall be coupled to theoutside through a material of low-heat conduc-tivity.

6.5 Jacket, a double-walled, air, or water-filledjacket. The calorimeter shall be insulated fromihe jacket by an air space. The sides, top. andbottom of the calorimeter vessel shall be approx-imately 10 mm from the inner wall of the jacketto minimise convection currents, Mechanicalsupports for the culoiimetcr vcwl shall provideus little thermal conduction us possible. Thejacket shall be cupuble of maintaining the tem-perature constant to within iO.I'C (*<)J'F) ofroom temperature at a calorimeter temperature2'C (4*F) below, and 2'C (4T» or more abose

441

4)0906-9 '. S6S XOd

nvm temperature throughout the determina-tion I' a Wr.iivr-fi l l ixi jacket is used, 11 shall him-j OCMV.C I'nr Miring the *aier at 3 uniform i*meu i i h nur.:niui%.) heat i r tput .

f t .6 I'licrnicmiters. used to measure tempera-ture tn the calorimeter and jacket *hall be ofany of the following t>p<rs or combinationthereof:

6.6.1 l.iyni<l'in'GltM Thwwnwrs, con-forming to the requirements for ASTM Ther-mometers 56C. 56F, UfiC. or M7C, as pre-svrirvd in Specification E I. The thermometersshall bv tested for accuracy against a knownstandard (preferably by the National Bureau ofStandards). For thermometers 5<>C and 56F, thecalibration should be at intervals no larger than2.0'C or 2,J'F over the entire graduated scale.The maximum difference in correction betweenany two test points shall be no more than 0,02'Cor'o.oyp. For thermometers I16C and H7C.the calibration should he at intervals no largerthan 0.5'C over the entire calibrated range. Themaximum difference in correction between anytwo test points Jiall not be more than 0.02'C

<j.f> 2 Ih'tkinuiw l)i(lcrt'iituil ThcrtmiHMt'ri.(glass-enclosed scale, adjustable) having a rangeof approximately ft'C in O.Ol'C subdivisionsreading upward and conforming to the require-men!1* f«r Thermometer 115C as prevrihed inSpculkation f: i. ma> K- u*eU. I'.aeh of tnesethermomclcr>> shall (x1 tested lor accuracs U|taiiisla k m i u n standard iprcfcruhl) b> ihc NationalHarciiu ill'Standards) at intcrsuls no larger thanI'C' over ihe entire graduated scale. The maxi-mum diflVrvncc in the correction between anytwo test points shall not be more than 0.02'C.

6.6.3 Oilwr Thvr>»i>iwivn, of tn accuracyequal 10 or better than 0,00IT. such as platinumresistance or linear thermistor thermometers aresatisfactory and may be used if properly cali-brated, A wheuistonc bridge and galvanometercapable of measuring resistance to 0.0001 0 arencccssury for use with 2i if platinum resistancethermometers.

6.' ThoniHuniiivAnvwriw—A magnifier isrequired for reading liquid-in-jjlaii thermometersu> one tenth of the smallest scale division. Thisvhull have a lens tind holder designed so as tointroduce no significant errors due to parallax.

6.K Samplr IttMer— An open crucible of plat-inum, quun/ . or acceptable naw-meial alloy,ftasv>mciul ul lu> crucibles are acceptable if, aftera few preliminary firings, the weight does not

change significantly between tests,6.9 /x""'"" " ""<' — The ignition wire shad he,

100 mm ol 'O.lfi-mm diameter (No. .14 B & Sgage) nickel-chromium alloy, (Chromel C) alloy.or iron wire. Platinum wire or palladium, 0.10-mm diameter (No. 38 8 & S gage) may he used.provided constant ignition energy is supplied.The length or mass of ignition wire shall remainconstant for all calibrations and calorific valuedeterminations.

6.10 l/fnilion Circuit, for ignition purposesshall provide a 6 to 16V alternating or directcurrent to the ignition wire. An ammeter or pilotlight is required in the circuit to indicate whencurrent is flowing, A step-down transformer, con-nected to an alternating current lighting circuit,or batteries, may be used.

6.11 BUM, used for the acid titration. shallhave 0, 1 -mL divisions.

6.12 .liwwW Cunirnlli-r anil Tvmpvrunm'Measuring Anvwrict. may be used.7. Rngcati

7.1 Rca/it'tit Water, conforming to Type II ofSpecification D 1 193. shall be used for prepara-tion of reagents and washing of the bomb inte-rior.

7.2 Punly of Rmgenus— Reagent grade chenvicals shall be used in all tests. Unless otherwiseindicated, it is intended that all reagents shallconform to the specification of the Committeeon Analytical Reagents of the American Chemi-cal Society, where such specifications are avail-able.* Other grades may be used, provided it isfirst ascertained that the reagent is of sufficientlyhigh purity to permit its use without lesseningthe accuracy of the determination.

7.3 /Menu1 Aeitf <C.H»COOH). shall be theNational Bureau of Standards benzoic acid. Thecrystals shall be pelleted before use. Commer-cially prepared pellets may be used provided the)are made from National Bureau of Standardshcn/oic acid. The value of heal of combustion oftvn zoic acid far use in the calibration calcula-tions shall be in accordance with the value listedin the National Bureau of Standards certificateissued with the standard.

7 4 \li-iti\l OrunKf, Mvthrf Rn(. nr Methyl

laiiipfli." Am. Owmicil Sue., Witftin|tun, IX'. I nrun the tniiA) of retgtnu mil Inii-o n> mr ^mrncn

Hnun. I) V»« Niitlftml CD., I*.' , Nfw Vori, NV, 4ml"I 'mini Suift Phirm»co()fii,"

442

# r aa \doo3~\3i.

/V/>/<- l/i(tnun>r. may be used to titrate the acidformed during combustion. The indicator usedshall he the same Ibr both calibration and calor-ific v.ilue determinations,

7 5 O\w>i. shall be free of combustible mai-ler Onl> o.\>jten m.mufaciured from liquid air,guaranteed 10 be greater than 99J <* pure,should be used. Oi>gen made by the electrolyticprocess may contain a small amount of hydrogenrendering it unfit without purification,

7 6 StH/iuni Cardinal? Standard Solution, so-dium carbonate (Na-COi) should be Jried Ibr Mh it I05*C. Dissolve JO.1* g in water and diluteto I L. One millilUrccif this solution is equivalentto 10.0 Btu in the nitric acid (HNOO tilration.

8. Surnpl*8.1 The sample shall be the material pulver-

ized to puss No. 60 (250-nm) sieve, prepared inaccordance with either Method D 346 for coke,or Method D 2013 for coal.

8.2 A wpjrate ponton of the sample shouldbe analyzed simultaneously for moisture contentin accordance with Method D20I3 and TestMethod D3I7J, so (hit calculations to otherbases can be made.

13 Sulfur analysis shall bt made in accord-ance with Test Method! 0 3177.

9. Safety Precaution!9 I The following precautions are reconv

mended Ibr safe calorimeter operation. Addi-tional precautions are given in RecommendedPractice E 144. Also consult the calorimeterequipment manufacturer's installation and op-•ruiing instructions before using the calorimeter.

9.2 The mass of coal or coke sample and thepressure of the oxygen admitted to the bombmust not exceed the bomb manufacturer's rec-ommendations.

9.3 Bomb pans should be inspected carefullyafter each use. Threads of the main closureshould be checked frequently for wear. Crickedor significantly worn parts should be replaced.The bomb should be returned to the manufac-turer occasionally for inspection and possibleproof firing.

0.4 The mygcn supply cylinder should beainipped with an approved type of safety device,such as u reducing valve, in addition to the needleva/vc and pressure gage used in regulating theoxigun feed to the bomb. Valves, gages, and

03286

gaskets must meet industry safety code. Suitablereducing \al\0sand adaptors for 3 to 4-MPa (300to JOO-psi) discharge pressure are obtainablefrom commercial sources of compressed gasequipment. The pressure gage shall be checkedperiodically for accuracy.

9.5 During ignition of a sample, the operatormust not permit any portion of her/his body toextend over the calorimeter.

9 6 When combustion aids are employed, ex-treme caution must be exercised not to exceedthe bomb manufacturer's recommendations andto avoid damage to the bomb. Do not lire loosefluffy material, such as unpelleied benioic acid.unless thoroughly mixed with the coal sample.

9.7 Do not fire the bomb if the bomb has beendropped or turned over after loading, or there isevidence of gas leakage when the bomb is sub-merged in the calorimeter water.

9.8 For manually operated calorimeters, theignition circuit switch shall be of the momentarydouble-contact type, normally open, except whenheld closed by the operator. The switch shouldbe depressed only long enough to fire the charge.

to. Standardization10.1 The calorimeter is standardized by com*

bustlon of benzole acid.10.2 Determine the energy equivalent of the

calorimeter for a specific temperature rise as theaverage of a series often individual runs madeover a period of not less than 3 days nor morethan 5 days. To be acceptable, the standard de-viation of the series shall be 6.5 Btu/'C(3,6 Btu/'?} or less (see Table 2). For this purpose, anyindividual test may be discarded only if there isevidence indicating incomplete combustion. Ifthis limitation is not met. investigate for thesource ol'the problem, correct it, then repeat theentire series to obtain a standard deviation withinthe acceptable limits.

10.3 Prtkvtluri1:10.3.1 Regulate the weights of the pellets of

heritoR* acid in each scries to yield approximatelythe same temperature rise as (hut obtained withthe coals titled in the same laboratory The usualrange of masses is from O.V to 1.3 g. Weigh thepellet to the nearest 0.0001 g in the sample holderin which it is to be burned, and record the weightas the mass.

10.3.2 Rinse the bomb, invert to drum, andleave undned. Add 1.0 mL of water to the bomb

443

UR3G0908VP

D 3286

pnur u> assembly ii>r a determination.KM \ Conncvi ;i measured length of ignition

w:re to Iftc ignition terminals, w i t h enough slackID allow the ignition wirv i» maintain contactw i t h the vmipie.

in,.1.4 Assemble the bomb and charge it w i thoxsjiett :o ,t consistent pressure between 2 to 3MPii (in lo W aim), t'his pressure must remain(he same lot eaeh calibration and each calorilk-\ulue determination. Admit the oiygcn slowl)mli> ihe bomb so as not to blow powdered ma-lenal from the sample holder. II' the pressurei'Mceds the spevil'ied pressure, do not proceedwi th iho combustion lnstyad._detaeh the (tilingconnection and eshaust the "bomb in the usualmanner, and OiwaM the sample.

10.3.5 Fill the calorimeter vessel (bucket) withthe measured (or weighed) quantity of wateradjusted from I.I) to 2.0'C lit) to 4.0'R belowthe jacket temperature, but not lower than 20'C(M*F^ (Note 4), Use the same mass of water ineach test weighed to ±0.5 g. For 2000-mL calo-rlniiflvn, ihv propvr quantity van be obtained byu<e of a volumetric fask calibrated 10 deliver:<KX> s 0,5 mL As the density of water variesuilh temperature, maki! suitable corrections ifthe water temperature saricc- from the temper^-Hire at which the llask was calibrated, Place theassembled bomb in the calorimeter msel. Checkihat no oxygen bubbles are leaking from thebomb, Place the calorimeter vessel in the jacket:v. on next the electrodes: place the stirrcn, thcr«mumi'tcrv and cover in position, Start \\w «ir-rvrts) and '.vniinwv to operate it (them) through-out the determination, H.umine the thermome-ters for liquid separation and correct any sepa-ration before prtKCcilinji, The starting tempera-ture should be within tO.J'C (±<).V''F) of thatused in the analysis of coal or coke samples,

Nun 4—The initial temperature adjustment willciiMjrv j iinjl tempi'ruture ili|hil> above thai of thejjcVei for 2<XX>-ml. caluntneien. Some upcnion preferj luwcr initial temperature so that thr (Inil i<mptratureii tlighlly hekiM thil of the jacket. Thii procedure i>.ilsii sati(fafii<fy. Whu-hev»r priViHlurc it uverf, the umepnx.«Jure ihould he uted in alt teiti, incluUmg nan-ilurOi/atiofl, \ unatt heater may he huili into the calo-rimeter w thai the denirai >turtin| tcmperuturc cm !xcuiily iill»irveit

NiiTt 5—Cheek all liquid-in-tlau ihcrmomrten atH'UH uaiiy f.ir any (jei'ccii. for rtitmple. traciccO gio«,tfIC

10.3.6 Allow 5 mm for attainment of equilib-rium; then record ihe calorimeter temperature at

l-min inte'-als for 5 min or until the rate ofchange has been nearly constant for 5 min. Usea magnifier when usinjj ASTM Bomb Calorime-ter Thermometers 56C or 56F, and estimate altof ilu1 ri'admjs (eU'tfpt thtw during the rapid-nse period) to the nearest 0.002*C or 0.005'F.Estimate ASTM Thermometers 115C. II6C. orI I"C readings to 0.001'C. and 25 U resistancethermometer readings to the nearest 0.0001 (J.Tap mercury thermometers (for instance with apencil) just before reading to avoid errors causedby mercury sticking to the w'alls of the capillary1'Ignite the charge at the start of the si.uh minuteand record the time. <, and the thermometerreading. /, (Note 6), Take the next two readings0.5 min and I mm after firing because of therapid rise. Record subsequent readings at I-mmintersals on the minute until the JilTerence be-tween successive readings has been constant for5 min. If the final temperature is above the bathtemperature, the temperature rises to a maxi-mum and then begins to fall. Record the time. /.ano the thermometer reading, /,, after the rate ofchange has become uniform.

NOTI A—The calorimeter water temperature musthe ut the same temperature (iO.OJ'C) for every deter-mination, at the time al linnj, if the Bureau ut' Minesmethod for radiation eormtten is to he used. See•\nm.'.\ AI..V

IO..V7 Open the cover and remove the bomb.Release Ihe pressure at u uniform rate, such thatthe operation will rvq»ir? not le»< than I mm.Open the bomb amt etamini- thr/ h«ir»if> interior.Oiward the test if unburned sample or sootydeposits are found. Wash the interior of the bombw'ilr) Oitlilled water containing the mratton indi-cator until the washings are free of acid, andtitrate the washings with standard sodium car-bonate solution.

IOJ.8 Remove and measure, or weigh, thecombined pieces of unburncd ignition (firing)wire and subtract from the original length orweight to determine ihe wire consumed in firingIf the wire is weighed, remove Ihe ball of oxidizedmcial from the end of each piece of w ire beforeweighing.

10.4 Cuh'iilattonx;10.4.1 TvmpvHUUtv KM— Using data ob-

tained as prescribed in IO..VA. compute the cor-rected temperature rise. /. as follows:

/ -r, -/ /•»• c1,-t- c, + r, (ii

444

SJ.Z03019B2.ZI* *• SCL8022.S R 3 0 0 9 0 9

-6 -9 XQM3X

« here:= 'corrected temperature rise. 'C or 'F.

/ = uimjj temperature reading Jt lime of sir-ing,

•* final temperature reading.('. = thermometer, emergent stem correction,

if required (see Nole 7 and Anne* At .4) .('. = thermometer selling correction, if re-

uuired (ice Note 7 and Annex A I.?), and('. • radiation correction (see Note 7 and An-

nex A 1.5).Null 7—\Viih all niercuri-m-jjlavs thermometer*,

n is n«wirv u> mal>c airrevuons ii'the total calorific\aiue n alteieJ t>> 5 Btu or more. This represents achange of O.OOI'O or (i.tHH'K in a calorimeter usingappd'MmjicK 2tXX) gof water, fkrkmanrrthermome-ivn> also require a setting correction and an emergentStem correction (Annex O..1 «n<l A 1.4). Solid-sumASTM Thermometers JfcC and J6F do not requireemergent Mem corrections if all tests, including sian-JardiMiion. are performed v»ithm ihc same 5,5'Ci !!)'(•! internal tf up*rating temperature* range hevondihn limit, a JilTercnfial emergent »t?m fofWHO« lAn-ncv \ I -t) mu« he annlu'd in the corm-te-J trnrocraturcnsv. i, in all tettt. including »umJjrdi7atiun A radiation(,'orrvctiun must he made in alt tnts. including sian-Jjrdi^alion.

10.4.2 TlitvimH'hi'niii-a/ f,'t^ffffiit»\f (ttC Ap-pendix XI)—Compute* thf following tor eachttMt:

c, * I'lirrrflinn for ihf hftit nf formation OfHNO<. in Btu. Each millilitfe of Stand-ard Na.CO? is equivalent to KM) Btu,und

I'.- s vorrwuon fur heat ol'cwnhuMion of fir-ing wire, in Btu (Note 8).

* <i.4i fltu/mm or 2,6 Btu/mg for No. .148 & S gage Chrome! C.

» 0.49 Btu/mm or .1.2 Btu/m| for No, .14HAS gage iron wire.

SIM i X—There it no correction Tor platinum wireprnt!<Jaf t'u1 ignition energy it cunilunt

104 .1 Computeihecatorimcterenergyequiv.ak-nt. A. by substituting in the following;

h - It//*) * i', 4 o|A C)» hew:/.' - calorimeter energy equivalent (Not? y),// - heat of combustion of lx-n«iic acid, as

it;rted in the Manorial Bureau of Standardscenifk'ate, Blu/lh in air.

u •» mau (weight in air) of hcn/oic acul. g./•i * lilration correction < 10,4,2),t'j » fuse vrire correction (10,4,2), and/ «* uirrected tempt-rature rise (10.4,1)

03288

NOTI 9—Using the units tnd corrections as given•n :<>•».I and 10.4,2. the energy equivalent of thecalorimeter is such thai the calonfic value of Ihe owlsample \vill f*obt,iifH-d directly in Bntish thermal unitsrvr poutij *hen ihe mavs sample ;s taken m grams.The units of the energy equivalent ar* therefure: (Blu/

10.5 Repeat the prcxredurc for a total of lendeterminations. Compute the standard deviationas illustrated in Table 2.

H. Rc5l*nd«rdlution11.1 Make checks on the encrg) equivalent

value aAer changing the oxygen supply, afterchanging any pan of ihe calorimeter, and at leastonce a month otherwise.

II.!.I [fa single new determination differsfrom (he old standard value by 6 Btu/*C (4 Btu/*F) the old standard value is suspect, therebyrequiring t second test.

11 .1 ,2 The difference between the two newdeterminations must nut exceed 8 Blu/'C (i Btu/», and the average oJ the two new determina-tions must not differ from the old standard bymore than 4 BlU/T (3 B(u/*F). If these require-ments are met. do not change (he calorimeterstandard.

If I 1 If ihi» r*<yiin»m<m(f jjt+n in 11.1.3 artnot met, two mort dnerminationi mint h? run.The range of the four value* must not exceed 14Bti»/*C «t Btu/*F), and the average of the fouinew determinationj mu$« not difler from the oldstandard value by more than 3 Btu/*C (2 Btu/T). If these requirements are met. do notthe calorimeter standard.

11.1.4 If the requirements given in 11.1 ..1 arenot met, a fifth and sixth determination must berun. The range of the six new determination*must not exceed I? Btu/'C (10 Btu/*F), and theaverage of the six values must not differ from Iheold slumlord value hy more than 2 Btu/'C (2Btu/*F), If these requirements are met. do notchange the calorimeter standard.

l l . t .3 If the requirements giN en tn 11.1.4 arenut met. four more determination* must he runlo complete a series of ten ru«v The range ofHwse ten resulis must not cuml 20 Btu/'C 112Htu/T). and the incriigir of the uin new valuesmust not differ from the ohl standard hy morethan | ntu/Vtl Blu/T). II (hesf riMuircmenisUK met. do not cliaityc the caloriiiU'tiT standard.

I I.I n Ifilic n-cjuii 'menis gi\en in 11.1.5 aremil im-i. tin- average value from ihc len new

z # '.f lR3009 IO

fHd CO:* fiS-6 -9 '• 962 a3ld003131 XOfc

0 328«

v a ' u c N must he used lor the new standard energycsi'.iisale'ii. proviccd tha t the standard d e v i a t i o n,if!l'e series does not osceed 10 Il iu ' ' ( ' '3 f' B t u /

I I 2 The s u m m a r y of ihe numerical require-t iMits .u each snge o! rcsundardi /a t tor : is givenHI 1'jNe 3.

12. Procedure Fur Coal iind Cuke Sample* (Note101

11.1 Thoroughly mix the analysis sample ofcoal or coke in the sample bottle and careCuIly'.scijih .ipproximateis I g of it into the sampleholder. The sample shall he weighed to the near-est u.oooi g. Make each determination in accord-ance w i t h the procedure described in 10,3.2through 10.3.8.

\uri i l l—For anthracite, coke. »nd coal of hi^haxh lontent. thai do not readily hum completely, oneyf the follow ing procedures are recommended, t/) I'heinside of the mmple hiildcr >s lined completely wi thignited aslx-stcn in a th in I JUT pressed well dimn intoihe angles, and the umple is ihen ipnnVJed esenls overthe surface of the asbestos. (.') The mass of ihe umplemay be carted to obtain good ignition. If the m«n its afted. n w ill be ntxnvirs to recalibrate the ealonmeterso that the water equivalent w i l l be hased on the umetemi'V'Mturi ' rix' as ihat obtained w i t h the new sampleweight. I.') A known amount uf hen/on acid may henused « r i h ihx sum ph.*. Prorvr allow jnve must be madel i > r the heat of uinihimion "I hen/oie acid when deter-nnn iH | j iiie calorific s jlue of the sample

Nun 11—|:(ir ihe mlorific salue oi coke, n is nee-< v i r \ 10 ux- 3 Mf'a (3d a im) pressure IW lx>lh stun-i..i,iu:iiiuii und analysis.

U T (Vtcrmtne the su l fur umtcii t of the urn-pic hs ,ni\ uf the procedures described in lesiM c t l u K l s I ) .1177.

13. Culculatmns (Noic 2\13 I Compute the corrected temperature rise.

/ as s l n m n in 10 1.1.

\ 11—( ' t i inpu ie the following lor each test:<•, « correction for ihe heal of formation of

UNO,, |lt» I'ach mHli T of standard\.Klium (.arKiiiale is eq ./lent tn 10.0MlU,

i fsir hviti of k ' t imbuMit in i i l ' ig-wire. ni».

\\ A S C'hromcl C wire.- 0.4') R tu /mm or 3,i Diu/mg for Nu 34

f) A S gage iron w i r e (Note Hi. andi1, • correction fordillercnce hvtween heat uf

formation of H-SO4 from the heat oflormmion H N O > . Btu.

• ;.V7 times pereeni of sul fur in samplelimn weight of sample. H-

14. CaloriCle Viluc(Note 12)14. | OViiu C'tihinth' 1'iy/m1— Calculate liie

gro^i. calorflic va lue (gross heat of combustion atconstant volume) Q, (gross) js follows:

C>, («rou> " |t//-.'l - r. - r. - ,-,)A- I »>

where:(J. (gross)

/•.'

. a

• gross calorific salue Utu/lb.» corrected temperature rise as cal-

culated in I .V I .• cnurg) equivalent calculated :n

10.4J.•« corrections as prest.T'rx.'U in I. VI

andi,' • mail of sitmplc, g,

14,2 ,Y(? Calorific I 'ulm1— Calculate the netcalorific \u lue (net heat of combustion at a con-stunt pressure). (},•, (ne t ) as follows

Q, (net) • </> (|ro«s) - IO..K> ill x MIwhere:^(n.-t) • net calorific valuv. Htu/l lvQ, (gross) • gross calorific \u luc. I t tu/ lh. and// - total

Nun 1 2— Tim calcululinn x've* cuUinliv \j|»e HIBlu/lK To nhtiiin eolorilic value in J 'H. we -Ni i iK ' tu l ixA ».

15. Report1 5. 1 The result* of the calorific value m;t\ he

reported on an> of a hunik-r ol'bas^, dirtcringfrom each other in the manner •'•••i moisture istreated.

I.VJ Use the percentage of moisture in thesample passing a No. 60 (250-um) siese, les iMethixl 13 3 1 73, to calculate the results of theanulssts sample to u dr> basis.

1^,3 I'roc'edures for convening ihe xalue or>-t.imcd on the analysis wmple to other haxs arc

l in MethiKl D 3 I M O .

I f«. I The follow iii|t iTiten.t v lmuM Iv used hninduing ihe .icicptyhli(> of results i» i .< ', proKt-h i l i l ) ) on split Ml-mcsh (l<i>.,ui» Mittples.

l^ I.I Hfi>nil<ihtlii\ — Duplicate results b>the same lahoraion using ilu- same o|X-rator ,indequipment , should not he considered susix-ct

44(.

a R 3 0 0 9 I I-s -y '. ase a3id(

O 3286

unless tlK'v dirtVr tn more lhan fO Blu/!h on a suspevi unless the two results differ by men; thanUr> basis. 100 Biu/ lb on u dry basil.

! f > , !.C Ki/>rtnliirihi(it\-— The results submit- 16 .1 3 0/«v— There should be no bias because:rtl b> two or more laboratories (different equip- the «iuipment u standardized with a eompoundmeni, operators, date of teM, untf different por- h a \ t n g u known heat of combustion.t ions ol ' the ume pulp) should not be considered

1 vHI t 1 V ilw

SitIIWtlful/AI)'Ufllnlff

iJ.t43ft71t|

It)MIM

\ >',i«v • I - 1\, In • i; I .>li,n

\. u ..in,. - • •

SUM.UM.Iv.ull.Mir.-

1 Illg • III** '^ J1 i jl.ifiv' • 4 l|i*N ; '

1 Inu tit^h,>njl uN* v'4\>nv

1 \BI.K 2 *>uiMhr4 O>ijl!o«H f<C.Jumn A

iHtu/lhl » i|/T)441":"""""mil441544014404440»444V44(0441!440*

'l*'l|li > 4JUI - 44IM

11 i - |il( iilumn HI1/')] 'Nd - tl'i.'u - 1 •«

.n7^;.>nT4. «::

Hlu/lh • J i.'iSl'n» Biu. Ih • I II i'ji '«

v Cilodiwirr StmrfaHlui

Column B

K'olumn *«U«)|i:*ui4d4

1012v

TJ

i' in| f

*'C\>lgm«C

iColumn BH

14449

225MItX)II

100144«I

940

' In i h i < I'xjmpl* ihr •.<!«« nf i'ntf|> (quoilrm irt ivpiml fo» t ttl\>nmt\tt ulihfiirJ fc> ih«. if ih* »nrr|» «iui>il<nt umull!ptird h) fhv ifmpcfjiu/t fiw in Orf/rr» Cflwv» p»' V«m trf wm|H*. Ihc cilonfk- »»tur uf ihr t«mpk »ill h» (>W4in«i in Bnn\ftI hftmil umu per pounj

Nun — Trti nl«n ««vrntifl| lihlr hitiiti fniuur wWilKjfulfun*'

.NumhM atRum

1

4A

10

Mmmum RmirofKnulli .

Hiu/T Blu/'F

» J14 XI T I U» Ij

Mnirnum Oiffirt*rmr hnwern T,

Blu/*C Bly/"K** »4*4 t.l»3 *2

' V jlUi't in llm UNf IIJM' Nvn muiufcU jftci vununuli jl> uUliim. jml jif iN'ffUnc cm |«iviwl> m « rjlut Inim I XIn 10

' V, <• mcfj»c nl iinninul sUitduiO jml V- « mrran1 i'fi l ink runt

447

9CL802i fHd• f l R 3 0 0 9 J 2

fi8-6 -9 f 962 a3ld003-|3i XOM

<SIr) 0 32M

ANNEX

(M»nd«lory Information)

At. THKRMOMKTUIC CORRECTIONS

M.I Thermometer Currtrttom\ I . I . i It it necesury to make the <oilo*mj individ-

ual corrmwnt if not making ihe cu"eciu»n» *ouldresult in »n ctiui>alent ctttrge wf 5.0 8w of mow.

A I . I . I CiJ/inreiiio'i CVrM'Mi'/i, shall be made in ac-cordance with the calibration certificate furnished bythe calibration authority.

A 1. 1. 3 Sftiinf Currvmun, necessary for (he B*ck-mann thermometer. It shall b« made in accordancewuh the directions furnished by the calibration author*ny.

A 1. 1,4 Dtt.krtntiat Kmerxt'rti Slftt C»rTKii<m. thecalculation of differential «<m correction dependsupon tht way tht thermometer *u calibrated and hewit it used. Two eonditioni ir* poiaible:

A 1 . 1 .4. 1 Tlun/WHirim CaMraitii in Total Immtr-sion tiHil Lisrd In Puntat /iHmi'rjioft—Thi* emtrjentitem concvtion l» rn»d* »» follow*:

Corrwion « C, • *,' (// - /.) (i/ * ', - L - Dwhere:O » em«r|tnt wm corrtvtlon.*,' • O.OUUI6 for thermometer* calibrated m 'C. »nd

O.OCXKW for ihermomwen cilibrmed m 'f.1. " knit readinf to which th* th*rmometer *« inv

mcnn tempvrttvrt of em«rvnt (Km,initial icmpcriiure re«dlfl|. tndflnul t<miwr«iurt reodin|.

At 1 —>K.\ai>tptv Awtume the point /.. totrve thermometer **<> immened wai I6'C': itk

j. /„ *n J4.li''C. iU Rnil retKimf. /A *«i^7 X7(i, the mean temperature of the emer|*nt item.r. »a»:6'C;Differential item corrccnon. C',• o,(xx)iAi:s- 24) cis * u - 16 -:A>• fiuowc,A 1. 1. 4.1 J'ht'Mihiwr/i''» ('tiltl'raitf] and I vet/ 10

I'tiriiul liHmrrutm. Hui <n u Uilkreiii Tt'tnpvruiwi; thantlir ( 'ttlil<rta\'<i rvmpvntiwv—^^n «m*ri«nt item cor-reuion it made ai followi:

C, •

emergent stem correction,O.OOOih for thermometer* calibrated in 'C. andi) (XXW fur thermometer* calibrated tn "F.initial temperature re*din|.final temperature readingobserved stem temperature, anditem temperature at which the thermometer *»•calibrated.

Nnir A, I 2—Kxumptt' Ajiume the initial readin|./,. *w UO'F, ih# final re»dm|, //. «« 86'F. »nd ihat the

stem tempemiure. i,. *»& 82'p. jnd .the culi'temperature, i,, *aj 71"K. then:

Differential item correction. C',• 0.00009 (86 - 80) (82 - '2)- 0.005'F,A 1.1 5 Ktniiunun ('<irwttiai\—These are uied to

calculate heat lou to '.he *ner jacket. They ire batedon the Oickmson focmultf.' th« Retnault-Pfaundlerfurmula.' or the U.S, Bureau of Mines method.' Theurn* method o( determining the radiation correctionmutt be uKd consistently m calibration and testiurcmems.

AI. I.}. 1 Dlckln.wn Formula:C, " - - n - fi (f- A)

iru-

where:C'/ * radiation correction.r, • rate of rise in temperature per mmute m

preliminary period.'i • raieofnte of temperature per minute in the final

period (tf temperutuir it Wllna. r, M net>ti\e)./, • firing temperature.', • final temperature, bemj tht first trmpvrature

after which the rate of chanit is cnnsuim./ - time at temperature. ',. mm.h • time at temperature. '• + <1.W u, - /,i.

mm, andi • time HI temperature. '/. min.

Al.l.J.J(", - nr, > kS

rudiatum cun-ectton.number of minutes in the vom-busnon peruxi.

u

k

f

r'i./i. h

' l)ivVin«in. It C, Hullcnn U > llurtau nl1 1. I"M. f. IK1*

f«- I *( l /2)d, » M ni1.averuye temperature dunnt thvprelimmao penod.iiveraic tempvraturtr Ounng the ft,nil penod.

\ s ,d1 'Mi'ilimiv of \iijlvm| imJ lf»Uft| Ciul tni ( nki-" I 1

H<'t,.iu,« Wtih'i HlitlrlitlltX X V t R t ' A . i'lft' p|i K.-l '

44K

duringand

ihe oortihusiion period.

ill'/ ,

A I . I . M Hitrruii in \tme> l/ffW— A table of ra-diation correction cun Se established so iliai oil) Ihe'.m;:jl and final reading are required «> determine theheal v j l u e ol an> fuel This ma> he done hy carmn|out a series of lesis ut i luinj the procedure ..leAcntxd inSection 10, using the following conditions, Regulatellie amount of sample, burned x> that n senei of deter-mination* 15 made in which different temperature rise*are uhimned For all determinations, keep the water

03286

jacket lemperaiure constant, fire the bomb at the samein i t ia l lemperaiure. and have the same time, / - /.eljpst ItJ s) between the ini t ial and final readings,CX'!*rrmn« the radiation corrections for each of theurnes of lemperaiure rites using the Dickinson method(see M I . J . I ) . or the Regnault-Pfaundler method lwv i . 1 . 5 . 2 ) . These corrections art constant for a given

temperature nse. From the series of readings a UbJe orgraph is plotted !0 show radiation correction versustemperature nse. Once the table or graph is established,the radiation corrections ctn be obtained from it untilthere is u major change in the equipment.

APPENDIXES

(Nonmonddtory Information)

XI. THEHMOCHEMICAI. CORRECTIONS

XI I KttfriQ• <tfFormation tit \tlrn ,4i it/— A correc-tion. 1-,. (10.4,: am) 13,2) is applied for the acid nirj-lion Thii corrnnion it based on the aitumptioni (,')that all ihe acid titrattd is HNO. formed b> the follow-m| reaction; ': N, <|) * >/t Oj Igl * "i H;O (1) - HNQtim 5(X) mal H;O). and (J1) thai (he ener|> of Cormaiionof' HNOi in approximately 500 moJ of uater underrximh cundilignj is minus J9.0 kj/mql.'4

XI I.I A corneniem concentration of Na;CO) no .Wa .V(20.<» | NajCOi/IWXi ml.) which »jve$ c, - 10multipJ) )'. where I' is the volume <>(' Ni^Oj inmilliliir'es. The factor 100 lO. W x 59 0 + !. JJn) n u>hv used lor caii.ulj|in| culonliv ^Jlue in Btu/lb Forother units wv Table X2.1. When H;.SO, iialwpr«em.j nun vrf ihe correciion for II;SO. 11 contained in ther, cMrri-viion and ihe remainder in the c» correviion.

XI J Knvrxrul fiirinutuiHulSiilfnne.Ivid— B> def-ini imn (X'v [Vfinnionj O 1 2 1 ) (he J/oss calorific valueit obtained when the product of the combustion ofsulfur in the sample u SOi (|). However, in Jduilrximb combustion proceuev all ihe sulfur is found uHsSOi in ihe bomb washinji. A correction o nee IX2)is applied for the iulfur thai is convened Ui HtSO<. Thislorreclion i» based upon (htf energy of formation ofH.-SO, in xiiudoni. such Jl *ill b«r present in Ihe fnimhji ihe end of j combustion. This ener|> is taken as

kJ/mol." A corrvctinn of 2 times >*>,() U/moJwas applied in ihe c. correction, to the »dd>

iiimai correction neceuir>' is 29}.0 - (2 time* 590) •177 kJ/mol. or * SI kJ/» of sulfur in the sample (55.21 ITTCJ weifhi of jamrjfe m trams times percent sulfurm sample). Thi* cium c( la be 2.1.7 times weight ofsample] in i/»m» limn percent sulfur in urn pie. Thefactor U.7(- 55 2/2.3261 for r, (see I.1.2) is 10 be usedfur calcuk««nf eakuific value in Biu/lb. For other units,see Appvndu X2. The values above a;e NiwJ on i cou!

«Niut 5 V sulfur jnd ihoui 5

The*ssump«ion isdso made that the H;SO< it dissolvedentirely in the water condensed dunng combustion ofihe ample."

XI. 2,1 If a l-tt sample of such a fuel is burned, iheresulting H..SOi condenwd with wmer formed on (hv»;ilis ol the bomb wilt hive a ratio of about 1 5 mul oi'wjter 10 I mol of H;SO«. For ihis concentration thecm-rv;) of the reaction S0> (\ ) * <t Oj (J) + HiO ( 1 ) •1 1;SO< (m I .< mol of HjO) under the conditions of thebomb pfwesi i» -2V5 kJ/mol." Baiin| the calculationup»n a «ni|Ht' of cumrwratiselj lurye sulfur contentreduces ilw rn»\>ible overall errors, because, for smallpercenia(!t'» tif sulfur, the corralion is smalkr.

X I . J /•'»<!• '/vniinHii I • w— Calculate the enerijsciininhuict) h> hurnin^ the fuse wire in jccordanci1« ith ihe directions lurnnhed h> the supplier ol the wireI ur evamplc. ihv energs of the combustion ol No 14H A S (Uiw Chromel (.' wire is 6.0 J/mj or approsi-maielv d.y.* J/mm. For calculating ('• for use in Cm 'and .». ihvse »i\e c; » 0,4) times lenyh i m m i ol wireor .•, • 10 times weight lm») of wire. The ener»sreyuircU m mell a plalmum wire is uinsianl for eaches.K'rinieni if ihe same amount of plaimum wire ismvd Ns ilw energy is small, iis eil'cci is ewnnallicatiiellvd uui in ihe relationship between ihe standard.nation csivnmcnts unU the culorilic \a luc dcivrmma-tii'ns. and it can tx- ne»lecied. The factors listed uho\etor c, ( 1 0 4 2 and 1.1.2) are suitable lor calculatingcaloniic value in Blu/lh, Fur mher units. s<.

from data m Vjiiun.il HurcjuVxe J7

C iI'him i)»ttt m llurrju »l

''Mini K \, jnd I'arkff ( •SiuJn->m lfcimhCjlnfimflf>i\ — li ir i iui i i iai i lSull 'unv Wid. "/!»•/ II HH \.il 17 !•»*)(P I'l

444

9 #

\2. RKPOH11NG RESULTS IN OTHKft I WITS

\; I Ki'/v/Ymjf Rt-MilH in J.mtci />('<• (jram\i '. 1 The grow caloric â luc ran he e\pr«ucd m

j;>u:.-s per gram, v-alones per grjm. or Bntish ihermalu n i t s IXT ;>iunU. The relationship* to»pcn ihev uni tsj re 41*en in Table I ,

X ? . i 2 Because the energy ot combustion lif III*' U c r v n u nijlcnu! is mcuiurcd and certified t>y theNalionj! f larruu of Standard! in joules per grim, themo5l jiMiihtlurYmru1 uttgc Ol' SP» reference mjwnulw o u l d iejj to I he CJlonlic sdlue of (hf f«e: in joules|x-r n/ji« To earn uut !hi^ procedure, we make changes. 'ui l incil u> \M \ through XM..V

\. : ' for cuk'ulutinitoncro nju iNaleni . substituteI'll :• lor 1'q ::

K m {Hll'n\ * i'|' * I!'!/' '-''

*licn' :!H' ni-jnip|» of'.hi? b>mK>' < ' i« fig 2' are thevi.IK ;is in I q 1 t f M C p t t h a t . . •/•.' » tnvr$> equivalent vmh unili uf

joules per wmpcnturc unit .// « heji of combuûon of reftrenic

material, '.nth j rnv of joules perj f jm weight m Jir (l/i from theecnifieate fur ihc ^BSand) and

ci . i';', and <•> ' • corrections. *uh un i t s I

y, tgr<i«)

A"

\2. 1 4 For ealeuUiing gross catonflc value. Juhsti-lull' Hi] ,V for Cq J'

<y, (gross) • KrA") - c,' - -V - iVV? (Vi*hvrc il>f tnruningn of ihe ivmixjli in t'o ,V arc the«nu- js m Pq 3 eietpt that:

• grow calorific value with unm ofjoulci per gram (weight in uir),

- energy equivalent. »uh u n i t s ofjoules per temperature u n i t , and

i - i ' . (•;'• -ind i')' • corrections. *>th un i t s ot' joules (x'eMNit I.' I)

XM.i I'm iwm:Xi . l .V: fwuiaMitf-* Uuplicat' results hy the

urnc larvirutury, using the unie oi> ralor und equip-ment. shoukJ noi he considered suspect u^lesi theyJilTer hy more than 1 30 J/g.

X2. 1 ,5,2 Ri'prodwihttitv— The results submitted hytwo or more laboratories (different equipment, operu-torv dale of test, and dilTerent portions of the umepulp) should not he considered suspect unless the resultsdiffer r>> more lhan 240 J/g.

I SBI > \M

By

MJ/mL nLuri»4.VNi<O»

trimsJ/mm lunjih immmCNy U » 4 S

HUH-

I U J /mni lrn>(fi Immiiil'S'o. ,U B A Sinnc mtn «irf

mimlrt>»lufOiriimeir »irc

1 (n tv uvtl m t q» J' urn* .V onJ)

M- i .»..-ii u* Vi < nvi fnf li'\n»i aitj MutenuH lairt iwpntittHi 'iM/m/inf i/n- vo/ii/n i ,*/ KHJ /x/d'/H /iîi ut« '»ti/ in < ruf/ii^ //iuiMii .<.•>« inivuimiit/ in Mn <taru/unl. i'stri i/iAn \iiHiifanlartttffti\lytuJri\tJ i*irf tlAtrmimuitHi tit ilii1 tuliiiin I>IM\' i tn»t njÂrt (/nj/ //!»• flit ii/ mfliKffmifKt lif »* A ''| 'l. Iff fKlUlfly llUU limit '

//in viinjurtl /i uiA;n/ /n mMftuf IM 111.1 Hint Hy lilt 'f \piM\ihlf Itthnirul ii'iniHHIi'r tinif mi>l hr rwitii'J r\'i'f\'lhe nw> ./«J// /«y 'i-inci/. rt/Aiv ftw/V»»«o/ «f tilMwt t'nur m/wiU'Wi ucr ciu/jirf i-ii/r<r /iv /ttvuuff ii/ /An \tuiujtinl <x Itn Muionul>iu«ift/'i/t u/ii/ stowM Iv <tiUif\\fii hi I.V/'.ir IlituJîiuiiift YiHif iimiMieil\ *ill mm,' tuiflul mHMile'uiiitt M u »icifi»« n/ i/vir\fn»MNfit\hnnalni>nimHer, xhiih I»M mui U//CKI/ // i i>n hvi iliiu ,\vuf mwimnwi /ruiw m« Mvirrd n Imr iitvunn run i/i.«././i»iMi' tint' I X - H I innH'/i fnr/ir <.S/ M < mnmiittv i>n .V/um/u/iA, / V / A /toir V. îlmJ^fî'U, ft IV 101

450

of HgO. 15 g of powdered K2SO4,L of H2SO«. Place the flask in an>sition and heat gradually. Then boilil the solution clears. Continue boil-additional 30 min. Cool, add aboutwater, cool below 25 °C, add 25 mLlution and mix to precipitate the,dd a pinch of zinc to prevent bump-s flask, and add a layer of NaOHufficient to make the contentskaline. Do not agitate the mixture.ly connect the flask to the digestionndenser. Have the tip of the con-icrsed in the H3BO3 solution (this: measured) in the receiver and thenlask to mix the contents thoroughly,the ammonia has distilled (at leastdistillate). Titrate with standard acidi indicator to violet end point.looilate the percentage nitrogen as fol-

t U :ived), % - (A X B) x 0.14

itres of 0.1 .V to 0.3 N H2SO« re-d for titration of the solution, andaliryofthe HjSO.,.

ort to the nearest 0.1 % the nitrogenic as-received sample.•a and Accuracyprecision of this method has notlined. Data are being sought thatble for use in developing precision

the validity of any patent rights asserted totah advised that determination of the validitynr own responsibility.

mittee and must be reviewed every five veanfor revision of this standard or for additional•eive careful consideration at a meeting oftHttts have not received a fair hearing you shouldladelphia. Pa. 19103.

Designation: 0 2974 - 84

Standard Test Methods forMOISTURE, ASH, AND ORGANIC MATTER OF PEATMATERIALS1

This standard is issued under the fixed designation D 2974: the number immediately following the designation indicates the •.ear -original adoption or. in the case of revision, the year of lasi revision. A number in parentheses indicates the year of last rrapprovaA superscript epsilon (<) indicates an editorial change since the last revision or reapproval.

1. Scope1.1 These test methods2 cover measurement

of the weight percentage of moisture, ash. andorganic matter in peat materials, including moss,humus, and reed-sedge types.

1.2 This standard may involve hazardous ma-terials, operations, and equipment. This standarddoes not purport to address all of the safety prob-lems associated with its use. It is the responsibil-ity of whoever uses this standard to consult andestablish appropriate safety and health practicesand determine the applicability of regulatory limi-tations prior to use.

1. Summary of Methods2.1 Method I—Moisture is determined by

drying a peat sample at 105*C. The loss in weightrepresents the total moisture content expressedas percentage by weight of the as-received sample.

2.2 Method II—This is an alternative mois-ture method which removes the total moisturein two steps: (/) evaporation of moisture by airat room temperature (air-drying) and (2) thesubsequent loss in weight of the air-dried sampleat 105'C. This method provides a more stablesample, the air-dried sample, when tests for ni-trogen. pH. cation exchange, sand content, etc..are to be made.

2.3 Ash content of a peat sample is deter-mined by igniting the oven-dried sample fromthe total moisture determination in a mufflefumance at 550*C. The substance remaining afterignition is the ash. and this includes mineralimpurities such as sand. The ash content is ex-pressed as a weight percentage of the oven-driedsample.

2.4 Organic matter is determined by differ-ence.

3. Apparatus3.1 Oven, regulated to a constant temperatui

of 105 ± 5'C.3.2 Muffle Furnace, regulated to a constar

temperature of 550'C.3.3 Evaporating Dishes, high silica or porci

lain, not less than 75-mL capacity.3.4 Blender, high-speed.3.5 Aluminum Foil, heavy-duty.3.6 Porcelain pan. spoons, etc.

4. Preparation of Sample4.1 Place a representative field sample on

square rubber sheet, paper, or oil cloth. Reduithe sample to the quantity required bv quarternand place in a moistureproof container. Wotrapidly to prevent moisture losses.

MOISTURE

5. Procedure—Method I5.1 Mix the sample thoroughly and place

test specimen of at least 50 g in an ignited anweighed (with fitted heavy-duty aluminum fccover) high silica or porcelain evaporating disof not less than 100 mL capacity. Crush solumps with a spoon or spatula. Cover immedately with the aluminum foil and weigh to thnearest 0.01 g. Dry uncovered for 16 h at 105"(Remove from the oven, cover tightly, cool, anweigh.

1 These test methods are under the jurisdiction of \STComminee O-I8 on Soil and Rock and are the direct rcsponbility of Subcommittee 018.18 on Peats and Related Matena

Current edition approved Oct. 26.1984, Published Dectmt1984. Originally published as D 2974 - ' 1 Last previous editnD 2974-71.

2 These test methods are currently undergoing an extensireview by Committee D-18.

497

D2974 Last ASTM 0««ignatio6. Calculation

6.1 Calculate the moisture content as follows:Moisture. % - [(.4 - Bt x IOOJ/.4

where:A = grams of as-received test specimen, andB = grams of oven-dried test specimen.

NOTE—In geotechmcal engineering the moisturecontent is commonly expressed as a proportion of theoven-dned mass. Care must be taken to indicate whichsystem is being used.

7. Procedure—Method II7.1 Use Method II when pH. nitrogen, sand

content, cation exchange capacity, etc.. are to betested. Mix thoroughly and weigh a 100 to 300-g representative sample and spread evenly on alarge flat pan. Crush soft lumps with a spoon orspatula and let the sample come to moistureequilibrium with room air. not less than 24 h.Stir occasionally to maintain maximum air ex-posure of the entire sample. When the weight isconstant, calculate the loss in weight as percentmoisture removed by air drying. Grind a repre-sentative portion of the air-dried sample 1 to 2min in a high-speed blender. Use the groundportion for moisture, ash. nitrogen, etc., deter-minations.

7.2 Thoroughly mix the air-dried, groundsample and weigh to the nearest 0.0Ig the equiv-alent of 50 g of test specimen on the as-receivedbasis. Determine the grams of air-dried sampleequivalent to 50 g of as-received sample as fol-lows:Equivalent sample weight.g = 50,0 - ((50 x percent moisture removed

in air drying)/100] .Place the weighed sample in an ignited andweighed (with fitted heavy-duty aluminum foilcover) high silica or porcelain evaporating dishand proceed as in Method I.

8. Calculation8.1 Calculate the moisture content as follows:

Moisture. % = (50 - B) x 2where:B = grams of oven-dried sample.

ASH

9. Procedure9.1 Place an uncovered (retain cover for

weighing) high silica or porcelain dish containingthe dried test specimen from the moisture deter-minations in a muffle furnace. Gradually bringto 550'C and hold until completely ashed. Coverwith the retained aluminum foil cover, cool, andweigh.

10. Calculation10.1 Calculate the ash content as follows:

Ash. i& -<cx IOO)A8where:C 3 grams of ash. andB = grams of oven-dried test specimen.

ORGANIC MATTER

11. Procedure1 1 . 1 Determine the amount of organic matter

by difference, as follows:Organic matter. % - 100.0 - D

where:D — weight percentage of ash.

REPORT

12. Report12.1 Report all results to the nearest 0.1 %.12.2 Indicate whether moisture contents are

by proportion of as-received mass or oven-driedmass.

13. Precision and Bias13.1 The precision and bias of these test meth-

ods have not been determined. Data are beingsought for use in developing a precision and biasstatement.

Standard Test MeSAND CONTEN

This test method covers deterpeat.

Formerly under the jurisdicticThis test method was withdrav

The Intern an Six. u'l \ far Tasting and Materials lakes no posilum respecting {he validity o/anv patent rights assarted in amnectltmit nil un\ Hem niiminmed in this standard i'sers of this standard are expressly advised that determination of the validity of any suchpatent neht\ and t/ic risk <il infringement of such rights, are entirely their own responsibility.

Thi! vumtard 1.1 VII/I/OY in revision at any lime by the responsible technical committee and must be reviewed every five vears andil nin r-evitvd. either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additionalstandards and ^hmild he addressed lo ASTM Headquarters Ymir comments will receive careful consideration at a meeting of there^ptm\ihle tei. annul cumminee, « hich wti may attend If you feel that vottr comments have not received a fair hearing volt shouldmake \inir I-K-M v knmn in ihif .*STM Committee on Standards, 1916 Race St.. Philadelphia. Pa. 19103

498

f t R 3 0 0 9 ! 7

Designation: 0 808 - 81 An Annncm NMCM Starand

Standard Test Method forCHLORINE IN NEW AND USED PETROLEUM PRODUCTS(BOMB METHOD)1

This standard ii issued under the fixed designation D 308; tbe Dumber immediately following the designation indicates theyear of original adoption or. in the cue of revision, the year of last revision. A number in parentheses indicates the year of lastreapproval A superscript epsiloo (<) indicates an editorial change since the last revision or reapprovaL

This method has been adopted for use by government agencies to replace Method 5651 of Federal Tea Method Standard No.79/fr.Attention a called to Note I on Safety and to the specific precautionary directions incorporated in the method.

1. Scope1.1 This method covets the determination of

chlorine in lubricating oils and greases, includ-ing new and used lubricating oils and greasescontaining additives, and in additive concen-trates. Its range of applicability is 0.1 to 50 %chlorine. The procedure assumes that com-pounds containing halogens other than chlo-rine will not be present2. Applicable Documents

2.1 ASTMStandards:D1317 Test Method for Chlorine in New and

Used Lubricants (Sodium AlcoholateMethod)2

D4057 Practice for Manual Sampling of Pe-troleum and Petroleum Products2*

3. Stannary of Method3.1 The sample is oxidized by combustion in

a bomb containing oxygen under pressure(Caution, Note 1). The chlorine compoundsthus liberated are absorbed in a sodium car-bonate solution and the amount of chlorinepresent is determined gravimetrically by pre-cipitation as silver chloride.

NOTE 1—Safety—Strict adherence to all of theprovisions prescribed hereinafter insure* against ex-plosive rupture of the bomb, or a blow-out, providedthe bomb is of proper design and construction and ingood mechanical condition. It is desirable, however,that the bomb be enclosed in a shield of steel plate atleast Vj in. (12.7 mm) thick, or equivalent protectionbe provided against unfoneeable contingencies.

4. Significance and Us*4.1 The method may be used to measure the

level of chlorine-containing compounds in pe-troleum products. This knowledge can be usedto predict performance or handling character-istics of the product in question.5. Apparatus

5.1 Bomb, having a capacity of not less than300 mL, so constructed that it will not leakduring the test, and that quantitative recoveryof the liquids from the bomb may be readilyachieved. The inner surface of the bomb maybe made of stainless steel or any other materialthat will not be affected by the combustionprocessor products. Materials used in the bombassembly, such as the head gasket and lead-wire insulation, shall be resistant to heat andchemical action, and shall not undergo anyreaction that will affect the chlorjis content ofthe liquid in the bomb.

5.2 Sample Cup, platinum, 24 mm in outsidediameter at the bottom, 27 mm in outside di-ameter at the top, 12 mm in height outside, andweighing 10 to 11 g.

5.3 Firing Wire, platinum, aonroximatelyNo. 26 B & S gage.

5.4 Ignition Circuit (Note 2), capaole of sup-plying sufficient current to ignite the nylon

' This method is under the jurisdiction of ASTM CommitteeD-2 on the Petroleum Products and Lubricant;.

Current edition approved by Aug. 28. I98i Pvwished Oc-tober 1981. OripnaUy published as D 808-44. Last previousedition D 80S -63 (1976).

In 1963. this method is adopted as standard without revision.'Annual Book ofASTM Standards. Vol 05.01.* Annual Book of ASTM Standards, Vol 05.03.

;U 01

NOTE :cuit shall bheld in cic

5.5 .Vvwhite.

5.6 Fil.pacny, m-

6. Reage:6.1 Pui

chemicalsotherwiseagents shaComm,Amer

its use widetermina

6.2 Puncated. refeto mean dpurity.

6.3 Nitrof concentand water.

6.4 Oxyand halogtsure of 40ously accel

6.5 SilvtL)—Dissolwater and >

6.6 SodiNajCO3/LNajCO3, 5.Na2CO3-l(

6.7 Whit7. Samplin

7.1 Takestructions u

7.2 Ensurepresentatthat the poris thoroughpie.8. Procedui

8.1 Prepc

348

A R 3 0 u y i B

D808

i Ninon* Stanon

m indicates the.the year of last

A Standard No.

ounds in pe-. can be usedig character-

live recoveryiy b« readilye bomb may

' ther material— combustioni in the bomblet and lead-i to heat andundergo anyne content of

am in outsidein outside di-t outside, and

.pproximately

ipableofsup-ite the nylon

^STM Committeents.)gl . Published Oc-

v< 44, Last previous

rd without revision.05.01.

.r

thread or cotton wicking without melting thewire.

NOTE 2—Caution—The switch in the ignition cir-cuit shall b« of a type that remains open, except whenheld in closed position by the operator.

5.5 Nylon Sewing Thread, or Cotton Wicking,white.

5.6 Filter Crucible, fritted-glass, 30-mL ca-pacity, medium porosity.

6. Reagents and Materials6.1 Purity of Reagents—Reagent grade

chemicals shall be used in all tests. Unlessotherwise indicated, it is intended that all re-agents shall conform to the specifications of theCommittee on Analytical Reagents of theAmerican Chemical Society, where such spec-ifications are available.3 Other grades may beused, provided it is first ascertained that thereagent is of sufficiently high purity to permitits use without lessening the accuracy of thedetermination.

6.2 Purity of Water— Unless otherwise indi-cated, references to water shall be understoodto mean distilled water or water of equivalentpurity.

6.3 Nitric Acid (1 + 1)—Mix equal volumesof concentrated nitric acid (HNO3, sp gr 1.42)and water.

6.4 Oxygen, free of combustible materialand halogen compounds, available at a pres-sure of 40 atmos. (Warning—Oxygen vigor-ously accelerates combustion, see Annex Al. 1)

6.5 Silver Nitrate Solution (50 g AgNOa/L)—Dissolve 50 g of silver nitrate (AgNOs) inwater and dilute to 1 L.

6.6 Sodium Carbonate Solution (50 gNajCOs/L)—Dissolve 50 g of anhydrousNajCOj, 58.5 g of Na^Oj-HjO, or 135 g ofNaiCOv 10 HjO in water and dilute to 1 L.

6.7 Whitt Oil, refined.7. Sampuai

7.1 Take samples in accordance with the in-structions in Practice D 4057.

7.2 Ensure that the sample is thoroughlyrepresentative of the material to be tested andthat the portion of the sample used for the testis thoroughly representative of the whole sam-ple.8. Procedure

8.1 Preparation of Bomb and Sample—Cut

a piece of firing wire approximately 100 mm inlength. Coil the middle section (about 20 mm)and attach the free ends to the terminals. Ar-range the coil so that it will be above and toone side of the sample cup. Insert into the coda nylon thread, or wisp of cotton, of such lengththat one end will extend into the sample cup.Place about 5 mL of Na2CO3 solution in thebomb (Note 3) and by means of a rubberpoliceman, wet the interior surface of the bomb,including the head, as thoroughly as possible.Introduce into the sample cup the quantities ofsample and white oil (Notes 4 and 5) specifiedin Table 1 (Caution, Note 6), weighing thesample to the nearest 0.2 mg. (When white oilis used, stir the mixture with a short length ofquartz rod and allow the rod to remain in thesample cup during the combustion.)

NOTE 3— After repeated use of the bomb for chlo-rine determination, a film may be noticed on theinner surface. This duDnes* should be removed byperiodic polishing of the bomb. A satisfactory methodtor doing this is to rotate the bomb in a lathe at about300 rpm and polish the inside surface with Grit No.2/0 or equivalent paper1 coated with a light machineoil to prevent cutting, and then with a paste of grit-free chromic oxide4 and water. This procedure willremove all but very deep pits and put a high polishon the surface. Before using the bomb it should bewashed with soap and water to remove oil or pasteleft from the polishing operation. Bombs with porousor pitted surface* should never be used because ofthe tendency to retain chlorine from sample to sam-ple.

NOTE 4—If the sample is not readily miscible withwhite oil. some other nonvolatile, chlorine-free com-bustible diluent may be employed in place of whiteoil. However, the combined weight of sample andnonvolatile diluent shall not exceed 1 g. Some solidadditive* are relatively insoluble, but may be satis-factorily burned when covered with a layer of whiteoil

NOTE 5—The practice of running alternately sam-ple* high and low in chlorine content should beavoided whenever possible. It is difficult to rinse thelast trace* of chlorine from the walls of the bomb andthe tendency for residual chlorine to carry over fromsample to sample has been observed in a number oflaboratories, when a sample high in chlorine haspreceded one low in chlorine content, the test on the

1 "Reagent Chemicals, American Chemical Society Spec-ification*. Am. Chemical Sot, Washington. D.C. For sua-

J Society, tet "Reagent Chemicals and Standards,"by Joseph Roun. D. Van Noctnad Co. lac^ New York.N.Y, tad th* "United State* Pharmacopeia."

' Emery Polishing Paper Grit No. 2/00 may be purchasedfrom the B*hr-Mannina, Co., Troy, N. Y. Chromic oxidemay b» purchawd Cmm J. T. Baker & Co.. Pmillip«ouij, N.J,

349

low-chlorioe sample should be repeated and one orboth of the low values thus obtained should beconsidered suspect if they do not agree within thelimits of repeatability of this method.

NOTE 6—Caotio*— Do not use more than 1 g to-tal of sample and white oil or other chlorine-freecombustible material.

8.2 Addition of Oxygen—Place the samplecup in position and arrange the nylon thread,or wisp of cotton, so that the end dips into thesample. Assemble the bomb and tighten thecover securely. Admit oxygen (Caution, Note7) slowty (to avoid blowing the oil from thecup) until a pressure is reached as indicated inTable 2.

NOTE 7—Cautfcm—Do not add oxygen or ignitethe sample if the bomb has been jarred, dropped, ortilted.

8.3 Combustion—Immerse the bomb in acold water bath. Connect the terminals to theopen electrical circuit. Close the circuit to ignitethe sample. Remove the bomb from the bathafter immersion for at least 10 min. Release thepressure at a slow, uniform rate such that theoperation requires not less than I min. Openthe bomb and examine the contents. If tracesof unburned oil or sooty deposits are found,discard the determination, and thoroughlyclean the bomb before again putting it in use(Note 3).

8.4 Collection of Chlorine Solution—Rinsethe interior of the bomb, the sample cup, andthe inner surface of the bomb cover with a finejet of water, and collect the washings in a 600-mL beaker. Scrub the interior of the bomb andthe inner surface of the bomb cover with arubber policeman. Wash the base of the ter-minals until the washings are neutral to theindicator methyl red. (The volume of the wash-ings is normally ia excess of 300 mL.) Takespecial care not to lose any wash water.

8.5 Determination of Chlorine—Acidify thesolution by adding HNOa (1+1) drop by dropuntil acid to methyl red. Add an excess of 2 mLof the HNOj solution. Filter through a quali-tative paper (if the solution is cloudy, the pres-ence of lead chloride (PbClj) is indicated andthe solution should be brought to a boil beforefiltering) and collect in a second 600-mJLbeaker. Heat the solution to about 140°F(60°C) and, while protecting the solution fromstrong light, add gradually, while stirring, 5 mLof AgNOi solution. Heat to incipient boilingand retain at this temperature until the super-

0808

natant liquid becomes clear. Test to ensurecomplete precipitation by adding a few dropsof the AgNO3 solution. If more precipitationtakes place, repeat the above steps which haveinvolved heating, stirring, and addition ofAgNCs as often as necessary, until the addi-tional drops of AgNO3 produce no turbidity inthe clear, supernatant liquid. Allow the beakerand contents to stand in a dark place for atleast an hour. Filter the precipitate by suctionon a weighed fritted-glass filter crucible. Washthe precipitate with water containing 2 mL ofHNO3 (1H-1)/L. Dry the crucible and precipi-tate at 110°C for 1 h. Cool in a desiccator, andweigh.

8.6 Blank—Make a blank determinationwith 0.7 to 0.8 g of white oil by following thenormal procedure but omitting the sample(Notes 5 and 8). Repeat this blank whenevernew batches of reagents or white oil are used.The blank must not exceed 0.03 % chlorinebased upon the weight of the white oil.

NOTE 8—This procedure measures chlorine in thewhite oil and in the reagents used, as well as thatintroduced from contamination.9. Calculation

9.1 Calculate the chlorine content of thesample as follows:Chlorine, weight %

where:P * grams of AgCl obtained from the sam-

pie,fl - grams of AgCl obtained from the blank,

andW » grams of sample used.10. Precision and Accuracy

10.1 The precision of this test is not knownto have been obtained in accordance with cur-rently accepted guidelines (for example., incommittee D-2 Research Report RR.-O2-1007,Manual on Determining Precision Data forASTM Methods on Petroleum Products andLubricants).

10.2 The precision of the method as ob-tained by statistical examination of interlabo-ratory test results is as follows:

10.2.1 Repeatability—The difference be-tween successive test results obtained by thesame operator with the same apparatus underconstant operating conditions on identical testmaterial would, in the long run. in the normal

antceetw<

1tw<tauem

IIIAbeAbeAbeAbe

Al.V

tioc

on:I

senoth'

nati

siorf

ternA

ble

7comof a.

7andsianrtspmate

350

Q R 3 0 0 9 2 0

est to ensureg a few drops

precipitationJS which have

addition ofmil the addi-o turbidity in>w the beaker

place for at.te by suction•ucible. Wash•ling 2 mL of• and precipi-ssiccator, and

eterminationMowing the

the sampleok wheneveroil are used.3 % chlorineeoil.chlorine in the5 wed as that

of the

I) X 24.74J/ W

-ora. the sam-

m the blank.

> not knownice with cur-ixample., in(.R:D2-1007,m Data forroducts and

.hod as ob-)f interlabo-

erence be-ined by theiratus underdentical test

* the normal

jjid correct operation of the test method ex-ceed the following values only in one case intwenty:

Chlonne. % Repeaubiliiy0.1 to 1.9 0.072.0 10 5.0 0.15Above 5.0 3 % of amount present

10.2.2 Reproducibility—The difference be-tween two single and independent results ob-tained by different operators working in differ-ent laboratories on identical test material

TABLE I QuiBffttoaf SiMffe ia* WUte Ofl

D808

would, in the long run, in the normal andcorrect operation of the test method exceed thefollowing values only in one case in twenty:

Chlorine, % ReproducibilityO.I to 1.9 0.102.0 to 5.0 0.30Above 5.0 5 % of the amount present

10.3 Cooperative data indicate that devia-tions of test results from the true chlorine con-tent are of the same order of magnitude as thereproducibility. '

TABLE 2 Gatt Pnom

Chlonne Content, %

2 and underAbove 2 to 5, inclAbove 5 to 10. inciAbove 10 to 20, inciAbove 20 to 50, incl

Weight ofSample, g

0.80.40.20.10.05

Weight ofWhite Oil. g

0.00.40.60.70.7

Capacity of Bomb. mLMinimum Maximum

Pressure/ atm Pressure.'* aim300 to 350350 to 400400 to 450450 to 500

38353027

40373229

""The minimum preuures are specified to provide suffi-cient oxygen for complete combustion, and the maximumpressures represent a safety rtaumment.

ANNEX

At. PRECAUTIONARY STATEMENTS

A1.1 OxygeaWarning—Oxygen vigorously accelerates combus-

tion.Keep oil and greise away. Do not use oil or grease

on regulators, gages, or control equipment.Use only with equipment conditioned for oxygen

service by careful cleaning to remove oil, grease, andother combustibles.

Keep combustibles away from oxygen and elimi-nate ignition sources.

Keep surfaces clean to prevent ignition or explo-sion, or both, on contact with oxygen.

Always use a pressure regulator. Release regulatortension before opening cylinder valve.

All equipment and containers used must be suita-ble and recommended for oxygen service.

Never attempt to transfer oxygen from cylinder in

which it is received to any other cylinder. Do not mixgases in cylinders.

Do not drop cylinder. Make sure cylinder is se-cured at all times.

Keep cylinder valve closed when not in use.Stand away from outlet when opening cylinder

valve.For technical use only. Do not use for inhalation

purposes.Keep cylinder out of sun and away from heatKeep cylinders from corrosive environmentDo not use cylinder without labelDo not use dented or damaged cylinders.

• See Compressed Gas Association booklets G-4and G4.1 for details of safe practice in the use ofoxygen.

The America Society for Testing and Material} lakes no position respecting the validity of any patent rights asserted inconnection wilt any Hem mentioned in this standard. Users of this standard are expressly advised thai determination of the validityof any sack patent rights, and the risk of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be relieved every five yearsand if not revised, either reapprovedor withdrawn. Your comments are invited either for revision of this standard or for additionalstandards and should be addressed to AS TM Headquarters. Your comments will receive careful consideration at a meeting of liltresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, 1916 Race St., Philadelphia, fa. 19103.

351

f l R 3 0 0 9 2 1

METHOD 9020

TOTAL ORGANIC HALIDES (TOX)


1.1 Method 9020 determines Total Organic Halldes (TOX) as chloride 1ndrinking water and ground waters. The method uses carbon adsorption with am1crocou1ometr1c-t1trat1on detector.

1.2 Method 9020 detects all organic halldes containing chlorine,bromine, and Iodine that are adsorbed by granular activated carbon under theconditions of the method. Fluorine-containing species are not determined bythis method.

1.3 Method 9020 1s applicable to samples whose 1norgan1c-hal1de concen-tration does not exceed the organlc-hallde concentration by more than 20,000times.

1.4 Method 9020 does not measure TOX of compounds adsorbed toundlssolved solids.

1.5 Method 9020 1s restricted toanalysts experienced 1n the operationthe Interpretation of the results.

use by, or under the supervision of,of a pyroly$1s/m1crocoulometer and 1n

1.6 This method 1s provided as a recommended procedure. It may be usedas a reference for comparing the suitability of other methods thought to beappropriate for measurement of TOX (I.e., by comparison of sensitivity,accuracy, and precision of data). There are three Instruments that can beused to carry out this method. They are the TOX-10 available from CosaInstruments, and the OX-20 and DX-20A available from Xertex-DohrmannInstruments.


2.1 A sample of water that has been protected against the loss ofvolatlles by the el 1 urination of headspace 1n the sampling container, and that1s free of undlssolved solids, Is passed through a column containing 40 mg ofactivated carbon. The column 1s washed to remove any trapped Inorganichalldes and 1s then combusted to convert the adsorbed organohalldes to HX,which 1s trapped and titrated electrolytlcally using a m1crocoulometr1cdetector.

3.0 INTERFERENCES

3.1 Method Interferences may be caused by contaminants, reagents,glassware, and other sample-processing Hardware. All these materials must ber- .ttnely demonstrated to be free from Interferences under the conditions of

analysis by running method blanks.9C - 1

Revision 0Date September 1986

HR3Q0922

3.1.1 Glassware must be scrupulously cleaned. Clean all glasswareas soon as possible after use by treating with chromate cleaningsolution. This should be followed by detergent washing 1n hot water.Rinse with tap water and distilled water and drain dry; glassware which1s not volumetric should, 1n addition, be heated 1n a muffle furnace at400*C for 15 to 30 m1n. (Volumetric ware should not be heated 1n amuffle furnace.) Glassware should be sealed and stored 1n a cleanenvironment after drying and cooling to prevent any accumulation of dustor other contaminants.

3.1.2 The use of high-purity reagents and gases helps to minimizeInterference problems.

3.2 Purity of the activated carbon must be verified before use. Onlycarbon samples that register less than 1,000 ng Cl~/40 mg should be used. Thestock of activated carbon should be stored In Its granular form in a glasscontainer with a Teflon seal. Exposure to the air must be minimized,especially during and after milling and sieving the activated carbon. No morethan a 2-wk supply should be prepared 1n advance. Protect carbon at all timesfrom all sources of halogenated organic vapors. Store prepared carbon andpacked columns 1n glass containers with Teflon seals.

3.3 Particulate matter will prevent the passage of the sample throughthe adsorption column. Particulates must, therefore, be eliminated from thesample. This must be done as gently as possible, with the least possiblesample manipulation, 1n order to minimize the loss of volatlles. It shouldalso be noted that the measured TOX will be biased by the exclusion of TOXfrom compounds adsorbed onto the particulates. The following techniques maybe used to remove particulates; however, data users must be Informed of thetechniques used and their possible effects on the data. These techniques arelisted In order of preference:

3.3.1 Allow the particulates to settle In the sample container anddecant the supernatant liquid Into the adsorption system.

3.3.2 Centrifuge sample and decant the supernatant liquid Into theadsorption system.

3.3.3 Measure Purgeable Organic Halldes (POX) of sample (seeInstrument manufacturer's Instructions for method) and Non-PurgeableOrganic Halldes (NPOX, that 1s, TOX of sample that has been purged ofvolatlles) separately, where the NPOX sample Is centrifuged or filtered.


4.1 Adsorption system (a schematic diagram of the adsorption system 1sshown 1n Figure 1):


AR300923

1.i 5s 5

E£VI

t

ec C

aSV)

2"5

.a

#


4.1.1 Adsorption nodule: Pressurized sample and nitrate-washreservoirs. (There are three Instruments known to ERA at this time thatcan be used to carry out this method. They are the TOX-10, availablefrom Cosa Instruments, and the DX-20 and DX-20A, available from Xertex-Dohrmann Instruments.)

4.1.2 Adsorption columns: Pyrex, 5-cm-long x 6-mm-O.O. x 2-mm-I.D.4.1.3 Granular activated carbon (GAC): F1ltrasorb-400, Calgon-APC

or equivalent, ground or milled, and screened to a 100/200 mesh range.Upon combustion of 40 mg of GAC, the apparent hallde background should be1,000 ng Cl" equivalent or less.

4.1.4 Cerafelt (available from Johns-Manvllle) or equivalent: Formthis material Into plugs to fit the adsorption module and to hold 40 mgof GAC 1n the adsorption columns.

CAUTION: Do not touch this material with your fingers. 01ly residuewill contaminate carbon.

4.1.5 Column holders.

4.1.6 Volumetric flasks: 100-mL, 50-mL.

4.2 Analytical system;

4.2.1 M1crocoulo»etr1c-tttrat1on system: Containing the followingcomponents (a flowchart of the analytical system 1s shown In Figure 2):

4.2.1.1 Boat sampler: Muffled at 800*C for at least 2-4 winand cleaned of any residue by vacuuming after each run.

4.2.1.2 Pyrolysls furnace.4.2.1.3 Mlcrocoulometer with Integrator.4.2.1.4 THratlon cell.

4.2.2 Strip-chart recorder.

5.0 REAGENTS

5.1 ASTM Type II water (ASTM D1193): Water should be monitored forImpurities^Interferents should not be observable at the method detectionlimit of each parameter of Interest.

5.2 Sodium sulflte (0.1 M): Dissolve 12.6 g ACS reagent grade NaoSOi InType II water and dilute to 1 L.

5.3 Concentrated nitric ac1d-(HNOO.


flR300925

&••*

1 Ti

ualio

n

3

5 .61*1355

I/)

rtjo

(SJ


f l R 3 0 0 9 2 6

5.4 Nitrate-wash solution (5,000 mg N03~/L): Prepare a nitrate-washsolution by transferring approximately 8.2 g of potassium nitrate (KN03) Intoa l-11ter volumetric flask and diluting to volume with Type II water.

5.5 Carbon dioxide (C02): Gas, 99.9X purity.5.6 Oxygen (03): 99.9% purity.

5.7 Nitrogen (N2): Prepur1f1ed.

5.8 Acetic add 1n water (70%): Dilute 7 volumes of glacial acetic addwith 3 volumes of Type II water.

5.9 Trlchlorophenol solution, stock (1 uL * 10 ug Cl"): Prepare a stocksolution by accurately weighing accurately 1.856 g of trlchlorophenol Into a100-mL volumetric flask. Dilute to volume with methanol.

5.10 Trlchlorophenol solution, calibration (1 uL * 500 ng Cl~): Dilute5 ml of the trlchlorophenol stock solution to 100 ml with methanol.

5.11 Trlchlorophenpl standard. Instrument calibration: First, nitrate-wash a single column packed with 40 mg of activated carbon, as Instructed forsample analysis, and then Inject the column with 10 uL of the calibrationsolution.

5.12 Trlchlorophenol standard, adsorption efficiency (100 ug Cl'/Hter):Prepare an adsorption-efficiency standard by Injecting 10 uL of stock solutionInto 1 liter of Type II water.

5.13 Blank standard; The methanol used to prepare the calibrationstandard should be used as the blank standard.


6.1 This method requires that all samples be run 1n duplicate.6.2 All samples must have been collected using a sampling plan that

addresses the considerations discussed 1n Chapter Nine of this manual.6.3 All samples should be collected 1n bottles with Teflon septa (e.g.,

Pierce 112722 or equivalent) and be protected from light. If this 1s notpossible, use amber glass 250-mL bottles fitted with TefIon-lined caps. Foilmay be substituted for Teflon 1f the sample 1s not corrosive. Samples must bepreserved by acidification to pH <2 with sulfurlc add, stored at 4*C, andprotected against loss of volatlles by eliminating headspace 1n the container.The container must be washed and muffled at 400*C before use, to minimizecontamination.

6.4 All glassware must be dried prior to use according to the methoddiscussed 1n Paragraph 3.1.1.


flR300927

7.0 PROCEDURE

7.1 Sample preparation;

7.1.1 Special care should be taken 1n handling the sample in orderto minimize the loss of volatile organohalldes. The adsorption procedureshould be performed simultaneously on duplicates.

7.1.2 Reduce residual chlorine by adding sulflte (5 mg sodiumsulflte crystals per liter of sample). Sulflte should be added at thetime of sampling If the analysis 1s meant to determine the TOXconcentration at the time of sampling. It should be recognized that TOXmay Increase on storage of the sample. Samples should be stored at 4*Cwithout headspace.

7.2 Calibration;

7.2.1 Check the adsorption efficiency of each newly prepared batchof carbon by analyzing 100 mL of the adsorption efficiency standard, 1nduplicate, along with duplicates of the blank standard. The net recoveryshould be within 5X of the standard value.

7.2.2 Nitrate-wash blanks (method blanks): Establish therepeatability of the method background each day by first analyzingseveral nitrate-wash blanks. Monitor this background by spacing nitrate-wash blanks between each group of eight pyrolysls determinations. Thenitrate-wash blank values are obtained on single columns packed with40 mg of activated carbon. Wash with the nitrate solution, as Instructedfor sample analysis, and then pyrolyze the carbon.

7.2.3 Pyrolyze duplicate Instrument-calibration standards and theblank standard each day before beginning sample analysis. The netresponse to the calibration standard should be within 3X of thecalibration-standard value. Repeat analysis of the Instrument-calibration standard after each group of eight pyrolysls determinationsand before resuming sample analysis, and after cleaning or reconditioningthe tltratlon cell or pyrolysls system.7.3 Adsorption procedure;

7.3.1 Connect two columns 1n series, each containing 40 mg of100/200-mesh activated carbon.

7.3.2 Fill the sample reservoir and pass a metered amount of samplethrough the activated-carbon columns at a rate of approximately 3 ml_/m1n.

NOTE; 100 raL of sample 1s the preferred volume for concentrationsof TOX between 5 and 500 ug/L, 50 mL for 501 to 1000 ug/L, and25 raL for 1001 to 2000 ug/L. If the anticipated TOX Is greaterthan 2000 ug/L, dilute the sample so that 100 mL will containbetween 1 and 50 ug TOX.


flR300928

7.3.3 Wash the columns-1n-ser1es with 2nitrate solution at a rate of approximatelyInorganic chloride Ions.

ml of the 5,000-mg/l2 mL/m1n to displace

7.4 Pyrolysls procedure;7.4.1 The contents of each column

being rinsed with the nitrate solution,from the atmosphere and other sourcesfurther analysis.

are pyrolyzed separately. Afterthe columns should be protected

of contamination until ready for

7.4.2 Pyrolysls of the sample 1s accomplished 1n two stages. Thevolatile components are pyrolyzed 1n a C02-Hch atmosphere at a lowtemperature to ensure the conversion of bronrinated trihalomethanes to atltratable species. The less volatile components are then pyrolyzed at ahigh temperature 1n an 02~r1ch atmosphere.

7.4.3 Transfer the contents of eachIndividual analysis.

column to the quartz boat for

7.4.4 Adjust gas flow according to manufacturer's directions.

7.4.5 Position the samplepyrolysis tube.

for 2 m1n 1n the 200*C zone of the

7.4.6 After 2 m1n, advance the boat Into the 800*C zone (center) ofthe pyrolysis furnace. This second and final stage of pyrolysis mayrequire from 6 to 10 m1n to complete.7.5 Detection: The effluent gases are directly analyzed 1n the mlcro-

coulometr1c-t1trat1on cell. Carefully follow manual Instructions foroptimizing cell performance.

7.6 Breakthrough; The unpredictable nature of the background bias makes1t especiallydifficult to recognize the extent of breakthrough oforganohalldes from one column to another. All second-column measurements fora properly operating system should not exceed 10X of the two-column totalmeasurement. If the 10X figure 1s exceeded, one of three events could havehappened: (1) the first column was overloaded and a legitimate measure ofbreakthrough was obtained, 1n which case taking a smaller sample may benecessary; (2) channeling or some other failure occurred, 1n which case thesample may need to be rerun; or (3) a high randon bias occurred, and theresult should be rejected and the sample rerun. Because 1t may not bepossible to determine which event occurred, a sample analysis should berepeated often enough to gain confidence 1n results. As a general rule, anyanalysis that 1s rejected should be repeated whenever a sample 1s available.In the event that repeated analyses show that the second column consistentlyexceeds the 10X figure and the total 1s too low for the first column to besaturated and the Inorganic Cl 1s less than 20,000 times the organic chlorine


flR300929

value, then the result should be reported, but the data user should beInformed of the problem. If the second-column measurement 1s equal to or lessthan the nitrate-wash blank value, the second-column value should bedisregarded.

7.7 Calculations; TOX as Cl~ 1s calculated using the following formula:

(C. - C3) + (C2 - C3)—-——~——-——— * ug/L Total Organic Hallde

where:

GI = ug Cl~ on the first column 1n series;

C2 • ug Cl~ on the second column 1n series;

03 - predetermined, dally, average, method-blank value(nitrate-wash blank for a 40-mg carbon column); and

V » the sample volume 1n liters.

8.0 QUALITY CONTROL

8.1 All quality control data should be maintained and available for easyreference or Inspection.

8.2 Employ a minimum of one blank per sample batch to determine 1fcontamination or any memory effects are occurring.

8.3 Verify calibration with an Independently prepared check standardevery 15 samples.

8.4 Run one spike duplicate sample for every 10 samples. A duplicatesample 1s a sample brought through the whole sample-preparation and analyticalprocess.


9.1 Under conditions of duplicate analysis, the reliable Hm1t ofdetection 1s 5 ug/L.

9.2 Analyses of distilled water, uncontamlnated ground water, and groundwater from RCRA waste management facilities spiked with volatile chlorinatedorganlcs generally gave recoveries between 75-100X over the concentrationrange 10-500 ug/L. Relative standard deviations were generally 20X atconcentrations greater than 25 ug/L. These data are shown 1n Tables 1 and 2.


3R300930

10.0 REFERENCES

1. GaskUl, A., Compilation and Evaluation of RCRA Method Performance Data,Work Assignment No. 2, ERA Contract No. 68-01-7075, September 1986.

2. Stevens, A.A., R.C. Dressman, R.K. Sorrel 1, and H.J. Brass, OrganicHalogen Measurements: Current Uses and Future Prospects, Journal of theAmerican Water Works Association, pp. 146-154, April 1985.

3. Tate, C., 8. Chow, et al., EPA Method Study 32, Method 450.1, TotalOrganic Halldes (TOX), EPA/600/S4-85/080, NTIS: PB 86 136538/AS.


HR30093

TABLE 1. METHOD PERFORMANCE DATA3

SpikedCompound

BromobenzeneBromodlchloromethaneBronx? formBromofortnBromoformBromofonnBromoformChloroformChloroformChloroformChloroformChloroform01 bromodl chl oromethane01bromod1ch1oromethaneTetrachloroethyleneTetrachl oroethy 1 eneTetrachloroethylenetrans-D1 chl oroethy 1 enetrans-D1 chic, methyl enetrans-01 ch 1 oroethy 1 ene

aResults from Reference 2.bG.W. » Ground Water.O.W. * 01 stilled Water.

Matr1xb

D.W.D.WD.W.O.W.G.W.G.W.G.W.D.W.D.W.G.W.G.W.G.W.D.W.D.W.G.W.G.W.G.W.G.W.G.W. •G.W.

TOXConcentration

(ug/L)

443160160238103110098112

, 10301001553741030101103098

PercentRecovery

95981101001409312089947976818673797578846360


*;*• •

flR300932

TABLE 2. METHOD PERFORMANCE DATA*

GroundGroundGroundGroundGroundGround

SampleMatrix

WaterWaterWaterWaterWaterWater

Un spikedTOX (ug/L)

68,5,5,54,17,11,

691210371521

SpikeLevel

100100100100100100

PercentRecovery

98,110,95,111,98,97,

991101051068989

aResu1ts from Reference 3.


HR3Q0933

M6THOO 9020TOTAL ORGANIC MALICES (Toxi

7.1.1 Takespecialcare In

Handling (ampleto minimize

volatile lose

7. i.2

7.3.2

Analyze nitrate-wasnBlank* to eataollin

repestaoillty ofnetnod Background

each day

Add sulflte toreduce residual

enJorine

7.1.2

7 ,3.3 DisplaceInorganicchloride

ion* By washingcolumns Mitn

nitrate lolut.

7.2.3 PyrolyzeduplicateInstrument—

calioratlon andblank standard*

aacn day

Score samples•t 4 degree* C

withoutneadspace

7.2.1

7.3.1

7.4.1

Protect column*from

contamination

Connectin serle*two columnscontainingactivatedcaroon

Cneckabsorption

efficiency foreach oaten of

carbon

7. 3. Z

7.4.3 Pyrolyzevolatile

copponent*in COi-rtcn

stnespnere atlow temeereture

Fillsample

reservoir: passssiapls tnrougn

activatedcarbon colunns

7.4.2Pyrolyteless volatile

compound* athigh temp in 0,rich stmeshpsre

o9020 - 13

Revision 0Date September 1986

MCTHOO 9020

TOTAL ORGANIC HALiocs(Continued

(TOX)

Tr«n«fercontent* of

••en column toquartz Do»t

for «n»ly«l»

7.4.4

7.5Analyze• ff lucnt

g«i« in icro-coulometric-

tltr«tlon ctll

Followinstruction*for e«s flowregulation

7.4.S Position• •MO I*

for 2 minin 200* C

zone

7.4.6

Advance oo»tinto BOO' Czone

o

Disregard•econa-column

v»lu«

Calculate TOXa* Cl-

9020 - 14Revision oDate September 1986

AR300935

METHOD 1010

PENSKY-MARTENS CLOSED-CUP METHOD FOR DETERMINING IGNITABILITY


1.1 Method 1010 uses the Pensky-Martens closed-cup tester to determinethe flash point of liquids Including those that tend to form a surface filmunder test conditions. Liquids containing non-filterable, suspended sol Idsshall also be tested using this method.


2.1 The sample 1s heated at a slow, constant rate with continualstirring. A small flame 1s directed Into the cup at regular Intervals withsimultaneous Interruption of stirring. The flash point 1s the lowesttemperature at which application of the test flame Ignites the vapor above thesample.

For further Information on how to conduct a test by this method, seeReference 1 below.


3.1 The Pensky-Martens and Setaflash Closed Testers were evaluated usingfive Industrial waste mixtures and p-xylene. The results of this study areshown below 1n *F along with other data.

Pensky-Sample Martens SetaflashI2 143.7 + 1.5 139.3 + 2.122 144.7 + 4.5 129.7 + 0.632 93.7 + 1.5 97.7 + 1.242 198.0 + 4.0 185.3 + 0.652 „ 119.3 + 3.1 122.7 + 2.5

p-xylene2 81.3 + 1.1 79.3 + 0.6p-xylene3 77.7 + 0.5* --

Tanker oil 125, 135Tanker oil 180, 180Tanker oil 110, 110DIBK/xylene 102 + 4b 107

75/25 v/v analyzed by four laboratories.a!2 determinations over five-day period.


AR300936

4.0 REFERENCES

1. 0 93-80, Test Methods for Flash Point by Pensky-Martens-Closed Tester,American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA19103, 04.09. 1986.

2. Umana, M., Gutknecht, W., Salmons, C.f et al., Evaluation of IgnltabHUyMethods (Liquids), EPA/600/S4-85/053, 1985.

3. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.


aR300937

7.3 REACTIVITY

7.3.1 Introduction

The regulation 1n 40 CFR 261.23 defines reactive wastes to Include wastesthat have any of the following properties: (1) readily undergo violentchemical change; (2) react violently or form potentially explosive mixtureswith water; (3) generate toxic fumes when mixed with water or, 1n the case ofcyanide- or sulflde-bearing wastes, when exposed to mild addle or basicconditions; (4) explode when subjected to a strong Initiating force; (5)explode at normal temperatures and pressures; or (6) fit within the Departmentof Transportation's forbidden explosives, Class A explosives, or Class Bexplosives classifications.

This definition 1s Intended to Identify wastes that, because of theirextreme Instability and tenancy to react violently or explode, pose a problemat all stages of the wast? management process. The definition 1s to a largeextent a paraphrase of the narrative definition employed by the National F1reProtection Association. The Agency chose to rely on a descriptive, prosedefinition of reactivity because the available tests for measuring thevariegated class of effects embraced by the reactivity definition suffer froma number of deficiencies.

7.3.2 Regulatory Definition7.3.2.1 Characteristic Of Reactivity Regulation

A solid waste exhibits the characteristic of reactivity 1f arepresentative sample of the waste has any of the followingproperties:1. It 1s normally unstable and readily undergoes violent change

without detonating.2. It reacts violently with water.3. It forms potentially explosive mixtures with water.4. When mixed with water, 1t generates toxic gases, vapors, or

fumes 1n a quantity sufficient to present a danger to humanhealth or to the environment.

5. It 1s a cyanide- or sulflde-bearing waste that, when exposed topH conditions between 2 and 12.5, can generate toxic gases,vapors, or fumes In a quantity sufficient to present a dangerto human health or to the environment. (Interim Guidance forReactive Cyanide and Reactive Sulflde, Sections 7.3.3 and 7.3.4below, can be used to detect the presence of cyanide andsulflde In wastes.)

SEVEN - 4RevisionDate September 1986

flR300938

6. It 1s capable of detonation or explosive reaction If it Issubjected to a strong Initiating source or 1f heated underconfinement.

7. It 1s readily capable of detonation or explosive decompositionor reaction at standard temperature and pressure.

8. It 1s a forbidden explosive, as defined 1n 49 CFR 173.51, or aClass A explosive, as defined 1n 49 CFR 173.53, or a Class 8explosive, as defined 1n 49 CFR 173.88.

9. A solid waste that exhibits the characteristic of reactivity,but 1s not listed as a hazardous waste 1n Subpart D, has theEPA Hazardous Waste Number of D003.

7.3.3 Interim Guidance For Reactive Cyanide7.3.3.1 The current EPA action level 1s:

Total releasable cyanide: 250 mg HCN/kg waste.

7.3.3.2 Test Method to Determine Hydrogen Cyanide Releasedfrom Wastes


1.1 This method 1s applicable to all wastes, with the condition thatwastes that are combined with adds do not form explosive mixtures.

1.2 This method provides a way to determine the specific rate of releaseof hydrocyanic add upon contact with an aqueous add.

1.3 This test measures only the hydrocyanic add evolved at the testconditions. It 1s not Intended to measure forms of cyanide other than thosethat are evolvable under the test conditions.


2.1 An aliquot of the waste 1s acidified to pH 2 1n a closed system.The gas generated 1s swept Into a scrubber. The analyte 1s quantified. Theprocedure for quantifying the cyanide 1s Method 9010, Chapter Five, startingwith Step 7.3.5 of that method.


ftR300939

3.0 SAMPLE HANDLING AND PRESERVATION

3.1 Samples containing, or suspected of containing, sulflde or acombination of sulflde and cyanide wastes should be collected with a minimumof aeration. The sample bottle should be filled completely, excluding allhead space, and stoppered. Analysis should commence as soon as possible, andsamples should be kept 1n a cool, dark place until analysis begins.

3.2 It 1s suggested that samples of cyanide wastes be tested as quicklyas possible. Although they can be preserved by adjusting the sample pH to 12with strong base, this will cause dilution of the sample, Increase the 1on1cstrength, and, possibly, change other physical or chemical characteristics ofthe waste which may affect the rate of release of the hydrocyanic add.Storage of samples should be under refrigeration and 1n the dark.

3.3 Testing should be performed 1n a ventilated hood.

4.0 APPARATUS AND MATERIALS (See Figure 1)

4.1 Round-bottom flask; 500-mL, three-neck, with 24/40 ground-glassjoints.

4.2 Stirring apparatus; To achieve approximately 30 rpm. This may beeither a rotating magnet and stirring bar combination or an overhead motor-driven propel lor stlrrer.

4.3 Separatory funnel; With pressure-equalizing tube and 24/40 ground-glass joint and Teflon sleeve.

4.4 Flexible tubing; For connection from nitrogen supply to apparatus.

4.5 Water-pumped or oil-pumped nitrogen gas; With two-stage regulator.

4.6 Rotometer; For monitoring nitrogen gas flow rate.

5.0 REAGENTS

5.1 Sulfurlc acid. 0.005 M; Add 2.8 ml concentrated H2S04 to Type IIwater and dilute to 1 L. Withdraw 100 mL of this solution and dilute to 1 Lto make the 0.005 H

5.2 Cyanide reference solution: Dissolve approximately 2.5 g of KOH and2.51 g of KCN In 1 liter of distilled water. Cyanide concentration 1n thissolution 1s 1 mg/mL.

5.3 NaOH solution. 1.25 N: Dissolve 50 g of NaOH 1n distilled water anddilute to 1 liter with distilled water.


flR3009l*0

STIRRER

FLOWMETER

0.005MH,S04-^

REACTION FLASK

ABSORBER

WASTE SAM?LE

Figure 1. Apparatus to Determine Hydrogen Cyanide Released from Wastes

SEVEN - 7Revision 0Date September 1986

flR3009M

5.4 NaOH solution, 0.25 N: Dilute 200 ml of sodium hydroxide solution(5.3) to 1 liter with distilled water.

5.5 Stock cyanide solution, 1 mg/mL: Dissolve 2.51 g of KCN and 2 g ofKOH 1n 1 liter of distilled water. Standardize with 0.0192 N AgNOs. Diluteto appropriate concentration so that 1 ml * 1 mg CN.

5.6' Intermediate cyanide solution; Dilute 50 ml of stock solution to 1liter with distilled water.

5.7 Standard cyanide solution, 5 mg/L: Prepare fresh dally by diluting100 ml of intermediate solution to 1 liter with distilled water, and store 1na glass-stoppered bottle.

5.8 Silver nitrate solution; Prepare by crushing approximately 5 g ofcrystals and drying to constant weight at 40*C. Weigh 3.3 g of dried, dissolve in distilled water, and dilute to 1 liter.5.9 Rhodanlne Indicator; Dissolve 20 mg of p-d1methylaminobenzal-

rhodanlne 1n 100 mL of acetone.

5.10 Methyl red Indicator; Prepare by dissolving 0.02 g methyl red 1n 60ml of distilled water and 40 ml of acetic acid.

6.0 SYSTEM CHECK

6.1 The operation of the system can be checked and verified using thecyanide reference solution (Paragraph 5.2). Perform the procedure using thereference solution as a sample and determine the percent recovery. A recoveryof 50X 1s adequate to demonstrate proper system operation.

7.0 PROCEDURE

7.1 Add 500 ml of 0.25 N NaOH solution to a calibrated scrubber anddilute with distilled water to obtain an adequate depth of liquid.

7.2 Close the system and adjust the flow rate of nitrogen, using therotometer. Flow should be 60 mL/m1n.

7.3 Add to the system 10 g of the waste to be tested.7.4 With the nitrogen flowing, add enough add to fill the system half

full. While starting the 30-m1n test period.

7.5 Begin stirring while the add 1s entering the round-bottom flask.

7.6 After 30 m1n, close off the nitrogen and disconnect the scrubber.Determine the amount of cyanide in the scrubber by Method 9010, Chapter Five,starting with Paragraph 7.3.5. of the method.


8.0 CALCULATIONS

8.1 Determine the specific rate of release of HCN, using the followingparameters:

A * Concentration of HCN 1n scrubber (mg/L)(This 1s obtained from Method 9010.)

L » Volume of solution 1n scrubber (L)

W = Weight of waste used (kg)

S = Time of measurement = Time N2 stopped - TimeN£ started (sec)

A • LR = specific rate of release » ———

W • S

Total available HCN (rag/kg) * R x 1,800.

7.3.4 Interim Guidance For Reactive Sulflde7.3.4.1 The current ERA action level 1s:

Total releasable sulflde: 500 mg H2$/kg waste.

7.3.4.2 Test Method to Determine Hydrogen Sulflde Releasedfrom Wastes


1.1 This method 1s applicable to all wastes, with the condition thatwaste that are combined with adds do not form explosive mixtures.

1.2 This method provides a way to determine the specific rate of releaseof hydrogen sulflde upon contact with an aqueous add.

1.3 This procedure releases only the evolved hydrogen sulflde at thetest conditions. It 1s not Intended to measure forms of sulflde other thenthose that are evolvable under the test conditions.


2.1 An aliquot of the waste Is acidified to pH 2 In a closed system.The gas generated 1s swept Into a scrubber. The analyte Is quantified. Theprocedure for quantifying the sulflde 1s given 1n Method 9030, Chapter Five.


y.

3.0 SAMPLE HANDLING AND PRESERVATION

3.1 Samples containing, or suspected of containing, sulfide wastesshould be collected with a minimum of aeration. The sample bottle should befilled completely, excluding all head space, and stoppered. Analysis shouldcommence as soon as possible, and samples should be kept in a cool, dark placeuntil analysis begins.

3.2 It is suggested that samples of sulfide wastes be tested as quicklyas possible. Although they can be preserved by adjusting the sample pH to 12with strong base and adding zinc acetate to the sample, these will causedilution of the sample, increase the ionic strength, and, possibly, changeother physical or chemical characteristics of the waste which may affect therate of release of the hydrogen sulfide. Storage of samples should be untierefrigeration and in the dark.

3.3 Testing should be performed in a ventilated hood.

4.0 APPARATUS (See Figure 2)

4.1 Round-bottom flask; 500-mL, three-neck, with 24/40 ground-glassjoints.

4.2 Stirring apparatus; To achieve approximate 30 rpm. This may :aeither a rotating magnet and stirring bar combination or an overhead motor-driven propeller stirrer.

4.3 Separatory funnel; With pressure-equalizing tube and 24/40 ground-glass joint and Teflon sleeve.

4.4 Flexible tubing; For connection from nitrogen supply to apparatus.

4.5 Water-pumped or oil-pumped nitrogen gas; With two-stage regulator.

4.6 Rotometer; For monitoring nitrogen gas flow rate.

4.7 Detector tube for sulfide; Industrial-hygiene type (100-2,000 ppmrange).

5.0 REAGENTS5>1 Sulfurlc add. 0.005 M: Add 2.8 ml concentrated H2S04 to Type IIwater and dilute to 1 L. Withdraw 100 ml of this solution and dilute to

1 L to make the 0.005 M H2S04.


flR3009i*l*

STIRRER

FLOWMETER

0.005 MHaSOr~

REACTION FLASK

WASTE SAMPLE

Figure 2. Apparatus to Determine Hydrogen Sulflde Released from Wastes


flR30.09l*5

5.2 Sulfide reference solution; Dissolve 4.02 g of Na2S-9H20 In 1.0liter of distilled water.Thissolution contains 680 ppm hydrogen sulfide.Dilute this stock solution to cover the analytical range required (100-680ppm).

5.3 NaOH solution, 1.25 N: Dissolve 50 g of NaOH 1n distilled water anddilute to 1 liter with distilled water.

5.4 NaOH solution, 0.25 N: Dilute 200 ml of sodium hydroxide solutionto 1 liter with distilled water.

6.0 SYSTEM CHECK

6.1 The operation of the system can be checked and verified using thesulfide reference solution (Paragraph 5.2). Perform the procedure using thereference solution as a sample and determine the percent recovery. A recoveryof 50% 1s adequate to demonstrate proper system operation.

7.0 PROCEDURE

The procedure employs a scrubber solution with wet method quantification.7.1 Add 500 ml of 0.25 N NaOH solution to a calibrated scrubber and

dilute with distilled water to obtain an adequate depth of liquid.

7.2 Assemble the system and adjust the flow rate of nitrogen, using therotometer. Flow should be 60 ml/mln.

7.3 Add to the system 10 g of the waste to be tested.7.4 With the nitrogen flowing, add enough add to fill the system half

full, while starting the 30-m1n test period.

7.5 Begin stirring while the add 1s entering the round-bottom flask.7.6 After 30 m1n, close off the nitrogen and disconnect the scrubber.

Determine the amount of sulfide 1n the scrubber by Method 9030, Chapter 5.7.7 Substitute the following for 7.2.3 1n Method 9030: The trapping

solution must be brought to a pH of 2 before proceeding. Titrate an aliquotof the trapping solution to a pH 2 end point and calculate the amount of addneeded for the 200-mL sample for analysis.

8.0 CAkCULATIONS

8.1 Determine the specific rate of release of H2S, using the followingparameters:


A » Concentration of H?S In scrubber (mg/L)(This 1s obtained from Method 9030.)

L « Volune of solution 1n scrubber (L)W • Weight of waste used (kg)S - T1»e of experiment - Time N2 stopped - Time

N2 started (sec)A • L

R » specific rate of release » ———W • S

*

Total available H2S (mg/kg) = R x 1,800.


ftR30Q9U7

METHOD 1110

CORROSIVITY TOWARD STEEL


1.1 Method 1110 is used to measure the corrosivlty toward steel of bothaqueous and nonaqueous liquid wastes.


2.1 This test exposes coupons of SAE Type 1020 steel to the liquid wasteto be evaluated and, by measuring the degree to which the coupon has beendissolved, determines the corrosivity of the waste.

3.0 INTERFERENCES

3.1 In laboratory tests, such as this one, corrosion of duplicatecoupons is usually reproducible to within 10X. However, large differences 1ncorrosion rates may occasionally occur under conditions where the metalsurfaces become passivated. Therefore, at least duplicate determinations ofcorrosion rate should be made.


4.1 An apparatus should be used, consisting of a kettle or flask ofsuitable size (usually 500 to 5,000 ml), a reflux condenser, a thermowell andtemperature regulating device, a heating device (mantle, hot plate, or bath),and a specimen support system. A typical resin flask set up for this type oftest is shown in Figure 1.

4.2 The supporting device and container shall be constructed ofmaterials that are not affected by, or cause contamination of, the waste undertest.

4.3 The method of supporting the coupons will vary with the apparatusused for conducting the test, but 1t should be designed to Insulate thecoupons from each other physically and electrically and to Insulate thecoupons from any metallic container or other device used 1n the test. Somecommon support materials Include glass, fluorocarbon, or coated metal.

4.4 The shape and form of the coupon support should ensure free contactwith the waste.


flR3009l*8

n

Figure 1. Typical resin flask that can be used as a versatile andconvenient apparatus to conduct simple immersion tests. Configuration of theflask top is such that more sophisticated apparatus can be added as requiredby the specific test being conducted. A = thermowell, B - resin flask, C =specimens hung on supporting device, D = heating mantle, E = liquid interface,F = opening in flask for additional apparatus that may be required, and G =reflux condenser.

1110 - 2Revision QDate September 1986

flR3009l*9

4.5 A circular specimen of SAE 1020 steel of about 3.75 cm (1.5 In.)diameter 1s a convenient shape for a coupon. With a thickness ofapproximately 0.32 cm (0.125 1n.) and a 0.80-cm (0.4-1n.)-d1ameter hole formounting, these specimens will readily pass through a 45/50 ground-glass jointof a distillation kettle. The total surface area of a circular specimen 1sgiven by the following equation:

A = -3.14/2(D*-d2) + (t)(3.14)(D) + (t)(3.14)(d)

where:

t - thickness.D = diameter of the specimen.d - diameter of the mounting hole.

If the hole 1s completely covered by the mounting support, the last term inthe equation, (t)(3.14)(d), 1s omitted.

4.5.1 All coupons should be measured carefully to permit accuratecalculation of the exposed areas. An area calculation accurate to +1% isusually adequate.

4.5.2 More uniform results may be expected 1f a substantial layerof metal 1s removed from the coupons prior to testing the corroslvlty ofthe waste. This can be accomplished by chemical treatment (pickling), byelectrolytic removal, or by grinding with a coarse abrasive. At least0.254 mm (0.0001 1n.) or 2-3 mg/cm2 should be removed. Final surfacetreatment should Include finishing with 1120 abrasive paper or cloth.Final cleaning consists of scrubbing with bleach-free scouring powder,followed by rinsing in distilled water and then 1n acetone or methanol,and finally by a1r-dry1ng. After final cleaning, the coupon should bestored in a desiccator until used.

4.5.3 The minimum ratio of volume of waste to area of the metalcoupon to be used 1n this test 1s 40 ml/cm2.

5.0 REAGENTS

5.1 Sodium hydroxide (NaOH), (20X): Dissolves 200 g NaOH 1n 800 ml TypeII water and mix well.

5.2 Zinc dust.

5.3 Hydrochloric add (HC1): Concentrated.

5.4 Stannous chloride (SnCl2).

5.5 Antimony chloride (SbCls).


flR300950

t


6.1 All samples should be collected using a sampling plan that addressesthe considerations discussed in Chapter Nine of this manual.

7.0 PROCEDURE

7.1 Assemble the test apparatus as described in Paragraph 4.0, above.

7.2 F111 the container with the appropriate amount of waste.

7.3 Begin agitation at a rate sufficient to ensure that the liquid iskept well mixed and homogeneous.

7.4 Using the heating device, bring the temperature of the waste to 55*C(130'F).

7.5 An accurate rate of corrosion is not required; only a determinationas to whether the rate of corrosion 1s less than or greater than 6.35 mm peryear 1s required. A 24-hr test period should be ample to determine whether ornot the rate of corrosion 1s >6.35 mm per year.

7.6 In order to determine accurately the amount of material lost tocorrosion, the coupons have to be cleaned after Immersion and prior toweighing. The cleaning procedure should remove all products of corrosionwhile removing a minimum of sound metal. Cleaning methods can be dividedMntothree general categories: mechanical, chemical, and electrolytic.

7.6.1 Mechanical cleaning Includes scrubbing, scraping, brushing,and ultrasonic procedures. Scrubbing with a bristle brush and m i l dabrasive 1s the most popular of these methods. The others are used incases of heavy corrosion as a first step 1n removing heavily encrustedcorrosion products prior to scrubbing. Care should be taken to avoidremoving sound metal.

7.6.2 Chemical cleaning Implies the removal of material from thesurface of the coupon by dissolution In an appropriate solvent. Solventssuch as acetone, dichloromethane, and alcohol are used to remove oil,grease, or resinous materials and are used prior to immersion to removethe products of corrosion. Solutions suitable for removing corrosionfrom the steel coupon are:

Solution Soaking Time Temperature»

20X NaOH + 200 g/L zinc dust 5 m1n Boiling

or

Cone. HC1 + 50 g/L SnCl2 + 20 g/L SbCl3 Until clean Cold


ftR30095I

7.6.3 Electrolytic cleaning should be preceded by scrubbing toremove loosely adhering corrosion products. One method of electrolyticcleaning that can be employed uses:

Solution: 50 g/L H2S04Anode: Carbon or lead

Cathode: Steel couponCathode current density: 20 amp/cm2 (129 amp/1n.2)

Inhibitor: 2 cc organic Inhlbltor/Hter

Temperature: 74*C (1654F)

Exposure Period: 3 m1n.NOTE; Precautions must be taken to ensure good electrical contact withthe coupon to avoid contamination of the cleaning solution with easilyreducible metal Ions and to ensure that Inhibitor decomposition has notoccurred. Instead of a proprietary Inhibitor, 0.5 g/L of eitherdlorthotolyl thlourea or quinolln ethlodlde can be used.

7.7 Whatever treatment 1s employed to clean the coupons, Its effect 1nremoving sound metal should be determined by using a blank (I.e., a couponthat has not been exposed to the waste). The blank should be cleaned alongwith the test coupon and Us waste loss subtracted from that calculated forthe test coupons.

7.8 After corroded specimens have been cleaned and dried, they arerewelghed. The weight loss 1s employed as the principal measure of corrosion.Use of weight loss as a measure of corrosion requires making the assumptionthat all weight loss has been due to generalized corrosion and not localizedpitting. In order to determine the corrosion rate for the purpose of thisregulation, the following formula 1s used:

Corrosion Rate (mmpy) '

where: weight loss 1s 1n milligrams,area 1n square centimeters,time 1n hours, andcorrosion rate 1n millimeters per year (mmpy).

8.0 QUALITY CONTROL

8.1 All quality control data should be filed and available for auditing.8.2 Duplicate samples should be analyzed on a routine basis.


AR300952


9.1 No data provided.

10.0 REFERENCES

1. National Association of Corrosion Engineers, "Laboratory CorrosionTesting of Metals for the Process Industries," NACE Standard TM-01-69 (1972Revision), NACE, 3400 West Loop South, Houston, TX 77027.

1110 - 6Revision 0Date SepteJEer 1986

SR300953

MCTHOO 1110

connosiviTy To*<A«3 ITECL

C7.1

A«*ci>ol* teat•OO«r«tuI

7.2

Fill eonttlntrKith «»««te

7.3

AQlOtl

7.4

M««t

07.6 Cl««n

coupon*By n«cnanlcal.cn«nlcal and/or•lactrolytIc

•«thod«

7.7• f fcctof cleaning

tr«>ta«nt enr««oving sound

7.m

O«t«r«ln«corrosion r«t«

( Stop J

O

1110 - 7Revision oDate September 1986

Horn t,U.S. ENVIRONMENTAL PROTECTION AGENCY \< m\jU ' U /v SASCLP SAMPLE MANAGEMENT OFFICE NX ' f^P.O. BOX 818 - ALEXANDRIA, VIRGINIA ~-^*'-PHONE: 703/557-2490 - FTS/557-2490




B. RSCC Representative; ANNETTE LAGE

C. Telephone Number; (301> 266-9180

D. Date of Request; NOVEMBER 8. 1991

E. Site Name; AIW FRANK. CHESTER COUNTY. PA



Analysis of /V building material samples (insulation material,etc.) for asbestos by EPA 600/M4-82-020, "Interim Method forthe Determination of Asbestos in Bulk Insulation Samples".


/Y unknown concentration building material samples (insulationmaterial, etc.) for the above analyses.

3. Purpose of analysis (specify whether Superfund(enforcement or remedial action), RCRA, NPDES, etc.):

RI/FS - ARCS III T_ T-FlA O3>/V

s


f tR300955


November 11 - 12, 1991.


Samples will be shipped by overnight air carrier as soon asthe laboratory assignment is received.

Number of days analysis and data required after laboratoryreceipt of samples:

/<4 calender days from receipt of last sample. The datawill be used to prepare a demolition specification sothat the buildings can be dismantled during the upcomingRI.

Analytical protocol required (attach copy if other thanprotocol currently used in this program):

Analysis to be done by EPA 600/M4-82-020, "Interim Methodfor the Determination of Asbestos in Bulk InsulationSamples".

8. Special technical instructions (if outside protocolrequirements, specify compound names, CAS numbers, detectionlimits, etc. ) :

Samples should be homogenized using a Freezer Mill ifpossible. Quantitate by point counting method. At least$ preparations and 400 points are required. Distilledwater is adequate for a method blank.

9. Analytical results required (if known, specify format for datasheets, QA/QC reports, Chain-of-Custody documentation, etc.)-If not completed, format of results will be left to programdiscretion:

Report in units of percent area. Types of asbestosfibers must be differentiated and quantitatedindividually. No minimum requirements are stipulated.Report all fibers, aspect ration >. 3:1 which are

10. Other (use additional sheets or attach supplementaryinformation, as needed) :

tAR30Q956



HR30Q957


Parameter Detection Limit _____ (+/-% or Concentration)

Chrysotile

amositecrocidoliteanthophyllitetremoliteactinolite

1*

1%1%1%1%1%

Report to nearest *.1% weight or volume


Audits Required ___ Frequency of Audits (Percent or Concentration)

Lab Blank 1 per 2£> Not detectedNBS standard . 1 per 2O q$ 90

1 per *<^ + 10%1 per J*


NBS Standard and lab blank - Reprepare and Reanalyze NBS Standardor lab blank and associated samples.

C0 r r e.c -A * £


Gregory L. Zimmerman - NUS Corporation - (412) 788-1080.November 8, 1991.


//-Please return this request to the Sample Management Office as soonas possible to expedite processing of your request for SpecialAnalytical Services. Should you have any questions or need anyassistance, please contact your local Regional representative atthe Sample Management Office.

HR300958

23SSOCOCDCDtoCO

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