sano Sampling and Analycal Wethods: Hydrazne, 108 [SEARCH U BSTENMERET ts: Gjissrcae Gpremerce GH EProrse ‘Occupational Safety & Health Administration We Can Help What's New | Onces ome || Womes | Ragubtons | Ererement | Date AStasles | Trarng || Aubatons || Newsom || Snatausnes | OSHA Fa ota wt cay gure ean ne mato eae cota. ime srcat G01) T4008 Ths praca te Seager arab Ok prs entn oan sean rao cre ee Sbs nthe sere oY OHH Hydrazine Related information: Chemical Samaling tune Math number 108 ae: ae Target concenation 10.90 (13 sam) and 1 ppm (1.3 mals) sta Pet: 1 ppm (13 m/m3) scan Tv: 1090 (13 m3) Procecure Samples are elcid loseoce by craving known vlumes ‘fair ough sampling eves corastog of three pace ‘assets, each cozalning two sure alé eased 37-mm ‘bss fle fats seperated by the rng secton. The lars are fetracted witha buffered TA endum slain, An abquot Sf the entra is dernatzed with a beralceye soliton to form benalavine fro" ary hyrazine in the sampes. The berzalaze Is cusrtated by LC using @ UW detect, Recommended ar le ‘20d sampling ate: 240 Lat Loumin elle quantitation int: 0.058 ppb (0.076 yam) ‘Standard ero of estimate at the target concentration: 7.59% at 10 ppb Target Conceriraton 5.234 at | ppm Target Concentration ‘tous of method eluted method. This method his been subjected tthe tstablshed ealaton procedures othe Organic Methods luton ranch, ‘ate: Febeury 1997 (Chemist: Carl. Hskamp Organic Methods Evasion Branch ‘OSHA Sal Lake Tecra Centar Satake Cry, UT 64165-0200 1. General Oscusson 1.1 Backoround 1.1.1 story n 1960, an alr samptng and anal procedure to determine hydrazine was valde bythe OSHA Analytica Laboratory. (at 5.1) The method (OSHA Matnad 20) is based ona field procure developed by the U.S, Alr Force that inves Jealecton of samples using sure ace coat Gas Crom R and colorimetric analss using r-methylamisobencldenyce (ef, 5.2) lSacause color procedure ae more susceptible fo nererress, an LC anal procedure wat azo developed by OS"A Method 20 where barzalzne, the reacuon procu: between heranne ard brzaléehi,s quarvated using a U datactr. Aer IMetned 20 was completa, suture act ested Gas Chor % acsorben tubes became commercaly avaiable, Since that time, the loss SLC (Sah Lake Tecsical Cover) has recoved cxmment fom other borates reporting kw exracsoneMicences and sample recavercs when using the commerce tubes. was deoded tht these cacerrs weld be nestgsted. Aso, becouse ACG omered te TLV rom 100 ppb 10 ppb (Re, 5,3) sce Method 20 was valated ard because OSHA may consider lowering the PEL _wmosha.govidisislcimethodslorganclorg08%org108.ninl unom 1 pom inthe fre, the methodology was evlusted at ower levels with est etrospheres 1 was rt possible for OSHA to generate hyerarine ts: mosphere when Method 20 was validate Soc thet ine, controle test armosphere generation syst mas consracod atthe OSHA SLTC that can be used to safely generate atmospheres fom tc compounds such as nya. A2.1- Pom atmosphere was goneraled and samples ware collcid using beth emmercal suri acd Weated Gas Chom sarang bes land saming tubes that wer prepared house. 2th samplers gave smi recoveries ut most othe hyératine was fund on the ror ols wool lug ofthe commercial bes. This dated that as prepared samplers are stored for an ended perc of me Beare use, some ofthe suture aod apparerdy migrates tothe lass weel plugs, turning the pug nto an effective sampler fr hyrazine snot known how eld the commercial ubes were for hs sud, bur thay ware probabl severel years ol. was fe that ine commercal ubes would be surabl, a5 lang asthe eass wool plug was eraced and analyzed alors with the treated Gas Chvor ft farther teste ata lovls of hydrazine showed poor recoveries and peer sample entrat silty rom acd sated Ges Covom R expecally forthe commer tbe. The poor recaveries ard tality may be at-bied ts the posible presence of ace metals 0 tie adsorbent, which was indicted bythe yellow clr of EDTA extracts othe ed rested Gas Clvom &. The EDTA execs fom the commercial tubes were deeper yebw than that rm he in-house prepared tubes, suagestng the presence of more met, nas sso fou that the comely prepared tubes hada highes acd catent than the rehouse tubes, which may De importa for recovery yes because the reaction between hydrazine and bezaldeyce Is sorewhat pi dependert An aerate sampling device lit woud avo the problems assodated with ace reated Gas Civom R was desabe, A promising canddate was 2 sampler [ores of suune so rented ase “be iter hat had been vakdated by te OSHA SLTC fora number of aromatic amines (Ref |S.) tal tests us sulfur acid Weated Gelman AE ita at pm kvel of hytrazineshomed colton efiencies, recoveries, and exracion eficences tobe essential 10%, The recovery ef yaratne collec ‘rm txt atmospheres is not gute 3s good at pb eves. nan ater ts erhance recoveries, fers weated with ether EDTA or Varin Cale or wi sure 3c were tested nth noiprovement. The fiers were alo treated wth afferent mineral ae, including hydroter, nic and phosphonic add, bur sua recoveries were no better ran when Jus sulfuric acd was used. Gelman A/E irs were used nthe methocs ‘or tomate amines ard may besa for hydrazine, but as fourd thatthe tke AB ier formed tiger seas te ier cassetes and they ao proves sihty beter eallecion eficences. The A ers can also be used fr aromatic amines lah no eer change i the methods. Improvemen’ were alto made tothe onalicalprocecie. ta fund that the roar temperature formation of bencalazine from hyrazne and beeldehye proceeded to competion ines han 30 minus at ebout 3.5 Aso ie use of EDTA disodium enhanced the stay of weracted srpls, so an aqueous EDTA dsodlum salon bere to v3 i used tm exract te er samples, Acetone nom used stead of methyl sleohol asthe solvent for benzalsenyae, The recommendes a velume was 20 Lin Metod 2, but in oger to obtaln aloe relable quotation lin and to havea ore Jemwerent sampling te of 4 hours 240 Lis the new recommended air volme, The areunt of barzalaze formed fom 2404. samples at por levels was fend tobe somewhat nscluble neti alcoal, bt was ound tebe much mere sll in acetone 1.12 Toxe effects (Ths sector sor nformaton only ard sheulé nat be akan asthe basi of OSA poley) werazre is earoregonc experimental animals and is a suspected human carcinogen. (e5.3) is coosive to the eyes, sn, and mucous membranes. the er ney, and hematoplete system ae he main aret organs ‘allowing repented exposures, (het £12) 1.3 Worcs | enposur -dravie sche sed a 2 chemical ermedate isthe procucson of agreuralchemial, spandex fas and antoxidars. Is also used as a rocee el oxygen Scavenger in oler water treater, polerzaton ctalys, Howling agent ard seavenger for gases. (Ref, 5.3) 11.4 Physical propertes (Re. 5.13 unless otherwise cenated) (AS number: 302-01-2 molealar weight: 32.06 bailing pon ise malig point 1c appearance Calories, oly, fuming Hq or whine crystals ens 2.2011 at 15°C molecule formula; aN vapor pressure: 13 KPa ot 20°C (Ret 52) Aas point UF (37.8°0) (open ep) coor penetrating, resemblng ammonia loner explosvelimt: 4.7% (Ref 6.9 ‘mens Oiamide; caring; tycrazine, anhydrous (O01); erasing, aquecus solton (O07) nase base; ryan (Pa); RERA waste number UL32 structural forma: HNN ithe anata concetratons throught ths methad are based on the recommended samping ard aalyical parameters. le loncanraions stdin ppb and pom ae referenced 25°C and 10,3 2 (760 ma) ARNough Bengaazine the all species anatze, all messes presen are ts of hyrazine 12 Limit define parameters 1.2.1 Deletion tnt of the nail procedure The detection ii ofthe anal proceie is 10.6 oa. Tis isthe aroun of anahte tat wit give response that significa diferent from the backround response of a reagent blank (Sectons 4 and 4.2) 122 Detection mt the overall procedure The detection tnt of te overall procedure I 5.48 np per sample (0.017 pp o 0.023 yn [Tiss the amount ef ana sped onthe sampler ‘hat wl gv a response that's sigan fret rom the backround response of 2 sampler Hank (Secions 4.1 and 4.3) 1.2.3 Relablequattaton lt The relate quareaton ims 18.3 9 per sample (0.058 ppb or 0.076 yam), This the amount of analyte spied ona sampler that il give a signal hats corsdered the ener init or precise uandtatve measurements. (Sect 48) 1.2 Precision (ancl procezure) The precsns of the aalycal procedure, measured as the pooled relate standard devaton oer concertraton ranges equtalerto O50 2smes te target [encanraten, are 0.26% and 009% based on the 1-pgb and the Ioppm target concentrations especie, (Scion 45) 1.2.5 Prekion (overal procedure) The pecions of the overall procedure tthe 95% conficence level or the amolent temperature storage tests are 214.8% ard 210.1% a 9.4 ppb and 1.06 pm respecinely, These lode an adlional 5% for sampling error. (Secon 8) 1.2.6 Recovery The recovery of hyracne ftom samples use 8 15-day storage test remained above 76% athe 10-pb target |concerraion wen the samples were stored at ambien temperatures, Phe recovery o yarn fom samples used in 320-807 storage test remained above 9636 a the I-ppm tarot concerraten when the samples were sored at ambien empeatures (Sscan 7) 1.2.7 Roprocucilty Sie samples a each argetconcesraton tat were cold from consoled test atmossheres, siong witha erat copy of hs procedure, wore submtac to an SLTC sarvce branch fe analy The samples were aralyzed ar 63 land 58 cays of storage atO°C forth 10-ppb and I-ppm target concentrations respectvel. One of the 10-pb target coreertraion| [amples was an aus, whe none ofthe remaining sample ruts devatd rm te teareical vale by more than the precsonssano Sampling and Analycal Wethods: Hydrazne, 108 reported in Secon 1.2.5, Section 4,8) 2. Sampiing Procedure 21 Apparatus 2.11 Samples rected ws pera sampling pp crate, with sonplg dee ached itn 155 ate feces torre TLE Some acre cans ace sng a sanping dev condiing of bo sire sees Son Gran Scenes p= Weber oer our ches (a Fd (pare no. 662C8)connined ina three-pece SAN (epee acres) paste NBO) ak Sete (amen pro, 39 or ere Cr Bera pr cushy Te ites re pepredy cng enh ra 0 of 0280 sur ceo Vsti acco pepe by arg 1 mo 364 Sie sls 250m. wen er met kot or done ot, Te ers ae feted encrusted mone chute san wed enn ove 10°C ten ants bason wed on ten ever ite epee 3-e sues mou Supper ps: Teo i spr he ck by tenn Sin The see ae sane i sr bn ard th ens oe ped wi pls hs 2.2 Reagents None requires 2.3 Teemique 2.3.1 Remove the plastic end pgs from he sampng device Immediately before camping. Samples are collected dosed ace, 2.3.2 |Atach the sampling evce othe samacg pump wth exe tug ad place the deuce nthe employee's beating zoe. Peston tne sampler so does rot impede work performance safety. 2.3.3 bo not pas the sampled air wough any hase o ubing before iene the sampling deve 2.3.4 immedatly after samp, sea the samling device wh plastic end plugs ad seal and Wieny with Form OSHAC21 seal. 23:5 Submit tees one bank with each sample set Dns shold be handled inthe same manner as samples, except no as [awn trough ther 2.3.6 Record smote volumes (Ines ofa) foreach sample Als litany compounds cosered pote nerferences tat cous be present in the sampling are, 2.317 any bulk samples are submited for ara, sip ther in separate conkers from te ar samples. 23.8 Sub the saroles to the laboratory for analysis as soon as posse afta sampling. If ely s unavoldabl, stare the samples at reduced temperate 2.¢ Sampler copay Sampler capacity is determined by measuring how much ar canbe sampled before bealcrough arate trough the semper cccurs, 2, the sampler capacty Is exceeded. Brcakhrcugh is coridered to occur when the effuer fram he sampler consis a conenfatin of anaie tats 5% ofthe upsteam concrtaton (3% breathvough). Tests fer Brekevous were performed ty simultaneously sampling a: 1 L/min rom a meranne atmosphere (815% Rt, 23.64C) at 2.1 ppm using four samplers. The sample flows were momenta nterupted and te bak ers were femoved and elaced wit es rs every teu ater sarping began over @ pri of ® hours. Te back ters were analyzed to determine the hyrazine corcentration i Ne leruert,atro time ding the B-how ets dd the eluent concentrations excted 5% of te wsream concentrator for ny of the four samplers, The ters re coated with an amour of suri acd that could teorecaly elect about 4.5 mg of hye. For a 240 ai sample, is woud be equal to 34.3 pom (18.8 msi") 2.5 Btractonefilency 2.5. The average eatracion oficences over the range of 0.5 t 2 times the target concentration are 98.7% an 98.936 based on tne S0-aps and I-pom levels respectively. Sects 433) 2.5.2 The exracieneffcrcy at 0.05 0.1 ard 0.2 tmes the target concerraton was found to be 97.7%, 97.5%, and 96.3% respecively based on the 10-pb level and 98.2%, 98.0%, and 9.6% respectely based onthe I-ppm lvl (Secion 4.9.1) 2.5.3, Both eeraces and exacted deriained samples a each target concentration remain stable fora last 24h, (Seon 48.2) 2.6 Recommended ar volume an sampling rate 2.6. For long-term samces, sample 240 Loft 1 Umin (-hsampes) 2.6.2 For sorta samples, sample 15 Lot ar a + Umin (25min sales), 2.6.3 When short-term samples are colectd, the a concerraterequvalen othe elable quarttation Imi becomes larger. Fer Jeample, the reliable quanttaton imi 0.93 ppb (1.22 ug) when 15 Lof aris sample, 2.7 terfrences (sampling) 2.7.1 snot known any cempourds wl severly wzerfre with the cllection of hcranine on sufuic aid ested ters. I goneral, any compound inthe sampled a har would reac: with sue acto decease the amour onthe fer wll ecrease he Beesevough volume. Ase, any compound that wil reac with hydrazine or eran sulfate a potential ierererce. 2.72 Suspected interferences shoul be reported ta the abratry wih suited samaes. 2.8 Safety precautions (sampling) 2.8.1 Atach the sampling equipment to the employe so that itil at irere with work performance or safety. 28.2 Folow all ssfety procedures tat appl tothe work area ber sampled 3. Aral Procedure 3.1 Apparatus 3.1.1 An system equlpped wih an ulravlet detector. A Henet:Pactard 1050 Sees LC cansstng ofa pumping system, 3 proerammeble variable wavelength detector and an autosampler was used in this evluan, 5.1.2 An elu capable of sepating the anal o ile rom at trferenoes, A 12.S-cm x nen kl Cwospher 100 RP-18 column (ewlet-Packard Company, pat no. 7982500564) ws used i Ws evaluation, [3.13 An elecronicirtegraor or some ater suilatie means of measuring peak areas or heights, A Waters Miler Networking [cormprer System was used ints evaluation, 3.14 Glass vals with Tefes®-tnod caps. Kinble ass Co, 7-nl dsposabl sctlton Vals (pr ne, 74502-7) and Thomas Seertic _wmosha.govidis/sltcimethodslorganiclorg08%org 108mlsano Sampling and Analycal Wethods: Hydrazne, 108 cans (at no, 2390-816) were use in the prepration of standards and extraction of smple ies, Noone Scene Co, 2-n Terget O°" ils nd cps (pat ro, CAD00-1 and CH000-54 respecte) were used Ine dervtizton of standards nd er lonract, 5.1.5 Hand held dspersrs (repeating ppetrs) capable of dlverng 05, 1.0 nd 5,0 mfr preparing and transfering standards and samste esac ae or depensing the deatzng sluon F spencers are no: availble, volume pipettes may be used etead 1.1.8 4 test tube rotator to mix the samples during the exracton step, 5.1.7 A berate corte. [3.2 Reagents 2.2.2 Hydranne or hyrarne soliton reagent arade, Aldrich Chemical (Mibraukee, WI Lot 211226N anhyrous hyiranne was ured inchs evaladon.Hyrazine i a Merl ne senstzer,muzage, and cacer suspect ager hati ready absored through sk Eis aso a covresie and combustble laud and a song reducing agent that shal be stores under nvogen. Standards ay array Be prepared rom reagent grade bervalazine oom a eagert grade hyranine say, such as hydranne yecnorice or hyetarne uta 5.2.2 Acetone, metnanal, and water, LC grade, The acetonitrile and methael used in tis evaluation were “Opts” brand rom Fisher Chemica (rir ew A) and the water was fom a iligore MI-Q water preston system, 3.2.3 Beraadehyde reagert grade, Aldrich Lo: 0362840 wes usedn this eels, Berealdetyde an rant, mage, senstze, and cancer suspect agent. ai and ght sensi and sould be store under nope. 3.24 Sodium phosphate, moncbasic mantyerate (NaHsPOe" HO), eager grade, ser Lot 704979 was wed ins evaluation. [32S EDTA dseauam, rom etyleredaminetetreacetc 2a, dsodum sak: ysrate, eager grade. Adc Lot 1487812 was used in is evaluation, 5.2.5 Phosphoric cd, esgent grade 5.2.7 baracten soliton, consisting 0 an aqueous Sluon ef 0.1 M NaPOy"H0]0.05 M EDTA Asodiun aahsted to pH 3.5 with prosphori acc. 13.2 Dervating sluen, prepared by dling 1.0 mL of benaldehyde to 300 mL with acetone, The derhatzing solution should be prepared fresh aly 3.3 Standard preparation 13.3.1 Prepare concentrated snk solitons by acrtaly dtng a known amour of hyrazin wth metho, Stock solitons ae sabe fo atleast days when reigeate, Standards cn aeratvely and more converierty be prepared from hyrazine [aryeroenrde, nyerannesufate or benzaezine, Stock tarda rm hyerazine salts shoul be prepared in wate, while standards trom berzalazine should be prepared in aceaniile. standards are prepared from one ofthe sls or Derzalazie, Ue apropits |cersion fact to determine the equate mass of hyerazie must be usec Fr example, hycacine sue (MW = 13012) © ised to make standards, the mass of hyrazine sulfate welghed out must be mpd by 0.2464 (32.06 + 130-12) to obtain the eautalnt mas of hei [3:2 Prepare aalyical standards by iecting merolter amouns of stock standard ino 7-ml als contain 5.0 mf extracion sakaion delveres om the same dsperser or pipet use to extrac samples, 13.3.3 erative te anata standards by tronslesring 1.0 mo the sardars to separate auzosample Was and adding 0.5 mt. of servtiing sluion to each val. Cap each val and shoke orf Seca to stain borough ming Allon the Wks ost trom tempeatre for at least 30 min before anaisis, Analyze the dervatzed standards by LC. 3.37 racket sample concentrations wth anevial standard concentrations, samples fl outside ofthe concetation range ot prepared sancards, prepare and analyze addoral sandards athe appropriate cncerraors tp ascertain the Inca of resoonse HTrecretcaly there's enough Berzalohe aed to the wa to prepare tandrésas high as 2.5 pom fer 2404 al samples (789, pulsanple). Aternadaly, sample concertratens are Niche an the Neches andar, tre exacts can be died wih exracton solder, and 1.0 mLalguos ofthe cluzed exracs can be derivatized and analyzed. 3.4 Sample preparation 3.4.3 Tranter ron and back fiers to nda 7m al [32 adds. 0 me of extraction sltono each val using the same dispenser or pipet = used for preparation of sancards. 2.43 Cap tne vials and mi them on rotate fr 30 min. [3.6 Centfige the sample Was fr 10 min at 200 rpm. [3.45 Dematze the samples oy rarsfring 1.0 mt of the contsfugd earacts to separate auosamser vil and adrg 0.5m of sernvting sluion to each val, Cap each val and shake tem for few seconds to obtain tho-oush bing, Allow te vast at om temperature frat east 30 min before aalysis. Analy te dervazed samples by LC. As a precautionary stp, the sample Jedracts shouldbe derated as Soon as posible ater they are extracted an centrge 3.5 Anais l35.2 UC condtons mobile phase: 67/3, acctontieymater ftw rate: 10mumin WW cotctor wavelength: 300. tector range: AUS for L-ppm target concentration 0.02 AUFS for {0-ppb target concentration injection votre: 5p colar: 125m x 4am id heospher 100 RAB _wmosha.govidis/sltcimethodslorganiclorg08%org 108mlsano Sampling and Analycal Wethods: Hydrazne, 108 . | Fowe 35.11. Cromatogram ofa 1Gppb target gure 351.2. chromatogram ata I-ppb target conezrizaton (3187) resample) standard obtained at concatraton (3187) vasampe) sandare 0.02 AUFS. Key: (1) excess berzldehyce, (2) cbainad at 2 ALES. Kee (1) excess Berzalanne (as hyaranne) benzaldetyde, (2) Serzlanne (as crane) 3.5.2 Peak areas or haloes ave measure by anirtgratoror ater sutable means 5.53 an enteral standac (ESTO) calirelion methed used. Calbation curves ae prepared by pting the amount of sna per sample versus peak eights or area cous of he Standards. Sample concentrations mus: be bracketed by Standards 3 a7 shes tchtate on sess cheep sine Fgre 25:11 Caltrain cave cna fom te Ague.2522 Catan cave oe om Gaolnabeasi Tre comtonsfelec 6 Oeanain tpbeas 2 Te cqonion he lne 3.6 wererences ara!) 3.6. Any compound that produces a response on 2 WV detector at 300 nm and has he some general reteson time of bergalizne a potential itererence. Possible interterences shoud be reported to the laboratory wi submited Sarpes byte nesta gers These inaferanes should be considered before sample are extracted 3.62 Lc parameters may be chanced to possibly creamer nerferences [5.63 When necessary, the lenty or purty fan alte peak maybe cofiemed with adtional anata ar, suchas wavelength ating. ean aid in thoteng appropriate wavelengihs to rato, he U spectrum of became gen n Saco 4 1, .7 calouatons The myeaine concentration for samples is ebained from the cabraton curve in terms of mierorans of hytevne per sample. The back iter of each samplers arazed primar to deerme if there was any breakthrough fom the rot er caring samping. a sigrfiart amour of ena found onthe back er, his fact shoul be reported wi) sample resus, ay [anaes found on the back iter, add othe arcu ound on the on Iter, This total amour then correct oy subtracting lene toa armour any found on the blank Thea conceraton cleat ung te following Ferma, ma = (a of hykacine per sample) / (of ar samplec)extracton eine] pom = ((mgm®)(24.46)]/ 32.06 = (mgin”)(0.7629) 3.8 Safety Precautions (arayacal) [3.8.1 Achere to the rues st vm in your Chemical gene Han. 38.2 Avid skin contac nd inhalation of al chemicals. 3.8.3 Wear safety lasses and a ab coat at all times whle the lab area 4. Bock ota 4.1 Determination of detection mis Detction mits (0), in genera, ae defined as the amour or concretion) of anal tat gives a response (Y.) tat signiicanty dere (tre stander evans (SO) Irom te baceorourerespose Yee. You = You = X50) |The aect measurement of Yq and SDs in chromatographic methods is typealy nconenient and difeut because Ye usualy |esremely low. Esimates ofthese parameters can be mode wth data otaines fromthe anal of 2 series of analyical andar or [Samples whose responses are nthe ny of the Background response. The regression curve abaned fra plot of retnemerk responce versus concentration of analyte wil sual be iear. Assumeng Sty andthe precision o ta abou the curve are sila, the senda errr of estimate (SEE) forthe regression curve can be substtuted fr SD inthe abowe equation, The fellbning Caleulatone dere a forma for Du oye = observed resporse Yes: = esimated response frm regression cue 1 = total no, feat pols k = 2 or linar regression uve |Acpoint Yo. on the regresson curve Ye = A000 + You 1A = anal senstivty (slope) Ierere Oo _wmosha.govidis/sltcimethodslorganiclorg08%org 108mlsano Sampling and Analycal Wethods: Hydrazne, 108 A sustutng SEE) + Yeq for You es 31S) a 4.2 Detetion mit of he anal procedure (OLAP) The DLAP is measured as he mass of al rroduced nto the |cromatographic cour. Ten anaical standards were prepared in equal descencing increments wih the highest standard Jortaining 3188 ng of hydrazine pr sample. Ths standard produces a peak approximately 10 mes te baci nls oa eagert ark, Standsrd, gus a veagert lang, were analyred andthe data ottaned were ured ermine the required paretes (and Se) fr the clelton othe LAP. Vales of 2222 and 7881 were obtained for A and SEE respectivay, The LAP was calculated w2 be 108 po a= Tle 42 ar or soning 5 conceaten ass once penkares ‘oaseroe) "a co ‘0.000 00 oF i Sie tote 2009 3 336 ies ame Be Sice ae Seve Ds yoo i iso" Ssa 8 bo lan es ae Be ene esi 50 153035022 Fgue'4.2. Phot ean om Tale 42:0 Be 1722 oa? aerrne he LAP 10.5 pm Tre ego of ite 12a? temeny = 2az0 = 395, 1.3 Detection mito the oval procedure (DLOP) The DLOP is measured as mass pe sarple and expressed as onal ai |cncenzatons, based onthe racoremenced samping parameters Ten samplers were spiked wi equal descending neererts of nya suc hat the highest sampler lasing was 3.88 nalsampe. Tiss he amour, when sped ona sare, ‘at would produce a peak approxima 10 tres the baseline seis fora sample blak These spked samplers, plus a samoe lark, were analyzed wit he recommended analycal parameters, an the data chained used to ealalate tne required parameters (A ana SEE) forthe caleulton ofthe OLOP. Values of 1559 and 2699 were cbaied er A nd SEE especie. The D.OP was eaeuated 0 be 5.48 na/sampl (0.017 pp 0.028 yam) rasle a3 ja Deccionunct te Swroce : rosso pe pesca ‘ane ors) : 9.000 o ‘es (ng) per Same ass $0 igre 43 tot ta Table 4.30 se B17 grr te LAP of 9 reat C7 12.75 19696 (ppb oF 0.023 pgim®), The equation ofthe line is ra ee PSS ams ba sone Ba sar 2 dar ihe oe ate oe 4.¢ Raabe quanitaton tt (204) The RQLs consierethe loner li or predse qundtatve measurements, Ris fetermined om the regression tne ta flvained fe the eakloton of the DOP (Secon 43). The RQLis defined as the amount arate tha gies a response (ped such tat agi ~ Yew = 10650) rector 1555) _wmosha.govidis/sltcimethodslorganiclorg08%org 108ml sistsano Sampling and Analycal Wethods: Hydrazne, 108 R= igure 44. Cheomatogram of te ROL Key: (2) enzaexine (es hyrenne) the RQ. was clelated to be 16.3 nlsample (0.58 ppd or 0.076 um’). The reaver ths levels $0.29 45 Precision enaycet method) The presen the anal procedure ate devin as he pooled ete Standard dewations (2503). Rete |standare deviations were determined from sx opiate injections of standards a 05, 0.75, 11.5, and 2 mes the get [cencanratons. Aer aesrng tat te RSDs ais the Cochran tx for Homageney at he 95% confidence lve the RSOps were eskuloted tobe 0.26% anc 0.05% based on the 1C-ppb end I-ppm target concentrations respecte ‘Teoe 452 Instrument Response Based on &10-opb Target Concentration vtargetcoren 05x 75K Le 1s 20% (ealsample) 158823903678 ae peakareas 3187300 5022900 e300 10115000 13192000 wes) Sr76v00 5002500 01100 10032000 13161000 1e4@00 Sooe200 15000 10035000 1214000 317s300 Soo1200 695100 10093000 13184000 rvao00 gsie00 6620900 s00u7000 13367000, 13176900 9596400 5627700 1026000 13130000, mean s17ssoo Sooo 1400010045000 12163000 ‘s mass 10S Toe 35545, a6 sb(%) 028 ozs 0200054 on |The Cochran test for homegeney borgest aso Sr = oro RSP%ase ¥ RSD. 25 1 RSD + ASDA. se + RSD%2y The ete value ofthe 9 statistic atthe 959% coidence lever fe variances, each associated wih sx abserations 0.5055. laecause the 9 satisic does nt exzed ths velue, the RSDs canbe considered tual and they canbe poled (RSOp)w ave an lestmatac RSD ‘forthe concensation range stl, ASD) = [RGN + RST, + ROE, + ASD s, + RODE) = 025% See+eHees Taste 452 Instrument Response Based on 8 I-ppm Target Concentration xeigetceren 05K OSE AS 20 ‘walsamoe)| ee 2390387 awl 7 peakareas 3338300 3030400 6688100 9868800 12721000, wes) 3321000 5035000 6672700 9877700 12741000 3324800 $0360 6674500 9977900 12744000 3aaeio0 —S039600 66e2700 9476900 12745000 333ca00 Soaar00 6684100 9879000 12746000 Saaceoo —Soaseno —6e8Se00 9990700 12752000 mean 23ssoo —sones00 6677900 9479000 12742000 Ey Daas SS Tides 6910672, 0%) 007 0109 ode 0.088 |The Cochran tt for omegenety largest aso? = eee = ose RSP%oe + RSD. 2m + RSD? + ASDA. se + RSD?ay The etal value of he 9 statisti at the 95% cotidence level or fe variances, each associated wih six observations, 0.5055. Because the g satis does ot exzed this velue, the RSDs canbe considered qua and they canbe poked (RSDp) ive an [estimates RSD forthe concnsraton renge side, _wmosha.govidis/sltcimethodslorganiclorg08%org 108ml asano Sampling and Analycal Wethods: Hydrazne, 108 ASD, = [SRS + RSI, + RSOE, + ASD, + RSD? pee+eHees 4.6 Precision (overall procedure) The precision of he overall procedure is determined fem the storage data in Seton 4.2, The eterminaton of the standard ero of estimate (SEE) fer a regression ne plated through the graphed storage data allows the incision af trage te as one of te factors afecting overall precision, The SEE sma tothe standard deviation, except ts @ measure of cisperson of data about a regression fre rstad of about a mean, R's determined withthe allowing emai Fn too a pos see, =[EWas-Vosl” 2 ev inearrepesion se i= runt reteson “Yne = cheered % recovery ata gen tine Yer: = estimated % recovery fem the regression Ine at he same gven time lan acstona 596 for pump err (SP) is added tothe SEER bythe action of variances to clan the oa standard eror of estate gee (SEE PHRF Hine precision atthe 95% cofidnce lve is obtained by muliphing the standard errr ef estirate wth pan eror nce) by 1.96 te stati om the standard normal devibaion a the 95% concence level). The 95% conigence tervals are craw 2p0ut ini respective ragressin ies inthe storage grap, ab shown Figures 47.1.2, 47.12, 47.21 and 4.72.2 The precksons ofthe overall procedure of 414.8% and 210.1% were cbaed from Foures 47.1.2 and § 7.2.2 for 10-ppb ard I-ppm target concentrations especialy 4.7 Storage test Storage samoles were prepared by samping 31 Lfmin om two arent contol tat abrospreres, [one 2 9:40 ppb andthe oes at 1.06 ppm. Bstn atmospheres were 2 approxmataly 2M Rb and a: room temperatures rangg rom 122-265 Sx samples each level were aralyzed immediatly afer gereraton,fteen were sared ina reirater 3 °C, an lineen were saved ina dosed crewer at amber temperatures of 20-25°C AL approximately tvee-cay wera, tee samples were selected Tam enc o the twa storage Sess foreach evel and aalyed Table 7.2 ‘Storage Test 2340 ppb time rofigerated storage ambient storage (ov) recovery (4). recovery (8) 0 07 RA MS OT TA mS 0 909 S49 gs? on SS 3 @0 S32 as ae G70 6G 6 0 5 se 9 90 BES uo 98 #3 G6 8 778 m3 913 oes E3396 752 eS ee ¢ i”) gape een ee a Fig.re 47... Refrgorated storage test at 92.40 ppb. Flgue 47.1.2. Amblont storage test at 9.40 pp. ‘able a72 Storage Test at 1,06 pom time refgarated storage ampere storane (cays) recovery (4) Fecvery (8) 0 62 978 58 6R 9TH SB 0 S55 958 7298S OER OTD 3 8 97 SS 98S GRAND 7 wea 932 1007 sas? 97.6981 a0 089975972963. 959 TA 3720978 99S GRA 8 2 996 984996 = 978984 MET _wmosha.govidis/sltcimethodslorganiclorg08%org 108ml atsano Sampling and Analycal Wethods: Hydrazne, 108 @ 8 Pd serps Pet eyes ef Bitleimanmsna se) Bedtietaesesnyiyezo ant sept Fae a724.Rofrondsorge WtetL06 Mgye 7.22 Ant sree eke om 4.9 Repreducty Reproducty samples ere prepared by sampling at 1 Limi from two cferent contol ses atmospheres, one at 9.40 ppb and the eter a 1.06 pn. Beth atmospheres were 3 approximataly 80% RH nc at room tamerazues ranging fer 22-26+C Sx samples foreach target concentration were submited to an SLTC sence branch for anal. Tne samples were stored or 63 and 38 days at O° before they were analyzed forthe 10-pob ard I-ppm rgetconcenation sales respeciely. One sample atthe &.40-pp evel was much lw than the ater sarses and conegeredto be an cule. is suspected mat ere Was a possblelesk on the seal ofthe sample casselte andthe manol adapter used inte contol test atmosphere generator. The rest the sampes cdot devete greater han the precions ofthe owes procedure determined Section 4.7, whch are 14.8% and 210.1% for the L0-pp and I-ppm target concentrations respective ‘Table 48.1 Reproducity Dat or 10-960 Samples sample rgreperted —ngespected —parcert devation 1 2097 “7 D6 2 29 gga 3 2406 ym 1-219 4 ded ye ha 86 5 {980 mo 8a é 284 gn 288 Table 49.2 ReproduebityData fer T-pem Samples sample uareported —_ppexpectad percent deviation 1 as m5 sas 2 ae as ious 09 3 2334 9958050 4 3402 3320 Bla 5 2864 wo? 8515 6 308, ms 9837 14.9 Cetractin efcleney ae sabi of extrac samples 4.9.1 Extraction efcerey The etractoneffciences (EE) for the two levels were determined by injcting standards ono suture acid rested ers wih amounts equvalert to 0.05 t 2 times he target concent ations. The average exracton effcencies ove" he lwerking range of 0.3 to 2 bres the target concentrations are 98.7% and, 93 based an he 10-ppb and L-ppm levels respecte ‘Table 43.14 atracton FicteneyEasedon 2 10-pp Target Corceration targetconen OSX Ok ORK 05K LOK 20% mass sphd(n9) 15743147 GOS 1574 3147 G95 FE (%) 982 984 950 84 9288S 961 980984 98 SBS BT 967 «77-970 BB 981 1004 564970953 GHD RS BS 1015 964 96.1 $80 980 S80 72 963 971 a9 97380 mean 77 «7S 963 8 981 992 Toble 49.1.2 [Extraction Eicency Based on 8 I-pm Target Concentration _wmosha.govidis/sltcimethodslorganiclorg08%org 108ml atsano Sampling and Analycal Wethods: Hydrazne, 108 xtargetcanen 0.05" 1K Oe OSX 10x 20% mass spked(pa) 1574 SLA7 6295. 1574 3187 6295 FE (OH) 953 985 sas 99 993 987 982 979 sae 980 980983 983 974 $5 982 982983 981 982 $85 984980983 983 981 $87 985 950 98.6 982 979 984-982 98S 98S ean 982 980 946 982 980 98.4 4.9.2 stay of extracted and exractederbatizes camps The stably of extracted samples at te bo target concentrations wee Investigated by anlying subsequent alquas ofthe exraced samples 24 ater the Seles wee ally ereced. Three othe lenractet samples (He fters were stl nthe was) were refrigerated, andthe ole tree wee alowed stand at room Iemperature one aboratory bench tp for each argetconcetation, Aliquots ofthe stored execs were alyzed with es standeres, The average percert change wos 0.8% ond 40.7% for sample exact that were rergirte, hd 40.3% and #0:39% fr tose stored at room temperate atthe 1-ppb and i-ppr target concertratons respective Table 49.241 Sttitty of Beratad Samples atthe 16-ppb Target Concerraton extracts refrigerated ‘extracts at room temperature ‘otal Eater intial Eater FE creda ference FE one day ference a) oo 68) 82806 oe 9840 e290 a7 580 Mea ei 93H 799830 (everaces) (avera0e5) sg2 soso sei 984403 Table 492.2 Stabile of erated Samples atthe [ppm Target Concerraton ‘extracts refrigerated ‘extracts at room temperature foal carer Intel EEafter FE onedey ference FE one day —_liflerence ) en) eso mo wah 0322 930987 a3 2 858 das 583 (overages) (verops5) 2 98907 see el a3 He stabi of exacted and derivatized samples was investigated by reanalzing te target concentration samples 241 after servetzaton and inal analyses. fer the ognal analses were performed, thee vals were recapped with new Septa whe the remaining tee retained ther puncured septa foreach target cncervation se. The samgles were eanaized wi resh stands the average percent change was -0.4% and -0.2% or sare that were reseled wih new sept, and =0.1% and 0.0% or hose that retained their pancured septa for serples atthe Ippb ad 10-pp target concentrations respectively ‘able 48.23 Stabity of Barats and Soriataed Samples at the 10-ppb Target Concerraten punctured septa replaced punctured septa retained veal FEaher lol EE oper FF oneday ference FE one day ference Ce) oO) 82-820 %e2 (980 03 m2 7 56 oe 80 m1 976 28 9398102 (averages) (averaps5) v2 978 04 se 980 ax Table 4.924 Stbity of erated and Oeratized Samples _wmosha.govidisisltcimethodslorganiclorg08%org 108. sorsano Sampling and Analycal Wathods: Hydrazne, 108 punctured septa replaced punctured septa retained ‘onal Eafe intial Eater cE oneday ference EE one day ference Cee) co oH) 03987 06 088 a2 0 8t 5088 2 m2 99a 4 BS 9870 (everaces) (aera955) m2 saa 02 see 988 oo 4.10 Quofatveanals& W spectrum for benzalane was obtained frm a Hevet Packard 1050 Series programmable variale [wavelength detector by injecting a andar using the same codons oven in Secon 25. con sis) Figure 410, WV spectrum of benzsazne In 67/33, acon wate, 5 References 5,05: Aralytical Methods Manual; Vel 2, Publ #4542, US. Department of Later, Ocupaional Safety and Heath Adinisraton; [05a Sat Lake Tectrical Cera: Salt ake Cy, UT, 199; Method 20: "drain; American Conference of Governmental Indust sini (CGI. Greet, OF 5.2. Suggs, 1,12 Lusts and JK Herman, Am. Ind. Hy. Assoc. 2, 1980, 41, £79-882, 5.3. Docurensation ofthe Threshalé int Values and Belial posure Ines, the, on TLvs and Other Occupational Bposize Velues- 1995- CD-Rom Publ. 99571W, American Conference of Govermeral instal igen (ACE): Cncnat, OF, 1995. 5. OSHA Arlyical Methods Manual, Vol 3, ubl. #4542, U.S. Department of Laer, Ocupainal Safety and Heath Adminstration; lose Sa Lake Tectrical Cer: Set Lake Cy, UT, 199; Method 57:4,4"Methlenedantve; American Canference of |covermertal industrial eis (ACG: indent, OF. 55. id, Metod 65: Benne, 3,3-Dichlroberane, 24 and 2,6-Tolveedaie, 5.6 bi, Metiod 7: e-Daniskie, 4,4-Metryerebs(-choranlig), o-Taine. 5.7 bi, Motiod 73: om, and Tole. 58, td, Metiod 78 Ohenyamine, esooropyaiine, [59. ba, Val 4, Metted 87", c-, and -Prenyenediaine /.0. id. Method 93: 4-Aminobiphery, -Naphtyarine and 2-aphtylaine s.1, stam, C2. “OSHA Method 105: m-Xyilenediamne and -Xyfenediamin’, OSHA Salt Lake Technical Center, unpublished Sateiske cy, UT a416s-0200, December 199, 5:12. Clayton, G.. and F.. Clay, Ed. Pats Indust Hygiene and Toxclogy’ hed, Vel. 2, Part Jn Wley 8 Sons ne. new Yar, W¥, 1994, 5.15, Lewis, Ro, Sr, £4, "Saxs Dangerous Properties of instal Mati”, the, Vo, 3; Van Nostrand [Reino Gos New Yor, NY, 1992 Wa. OSHA.gov _wmosha.govidisislcimethodslorganiclorg08%org108.Ninl wm