Document KGYm5rLXeo4z45qbpO1ywv9eK

Am Ind Hyg Assoc J 43(8| 60S-621 (1982) The history of development and validation testing of passive dosimeters is reviewed. Theoretical consideration including possible limiting factors or interferences, are presented. Laboratory and field validation tests ai critically reviewed and results are presented for comparative purposes. Evaluation of available data indicates th. passive dosimetry, with some exceptions, is an acceptable method for monitoring gasses and vapors Mo importantly, passive systems appear to be as reliable as the now accepted active sampling systems Passive dosimetry -- state of the art review VERNON E ROSE and JIMMY L PERKINS S< Root of Puhlir Health, University of Alabama in Birmingham. Birmingham AL 36?94 introduction Rt\ oj!nnion cv<ilu.n ion and com t ol ate the i ot net stones o( persona I passiv c dosimclct peisonal bet.him iic.inh, .. 1 hi a ppl icat ion ol that tin \l ut v ol seinin' a tut a 11 k now n as bv the worker in close piosimitv to tin lucathnm on i tu) nsl t ta I h\ g ittic I It esc t hrec tasks, howon. ,m no I on per passive because theie o no pump to move tin an mi tic eminent domain ol the industrial hygienist In the past collector wbtvli cquatts to Itvei v ,i' \ bi a t n > 11 ami i , divide, a ptolileratton of lumittf in the recognition of nance pm hie ms Some quai t c I vv it I. t h. 11 t m d t'si nii't " uoikpl.nc hazards has been made widclv available to putists ptc'fetnng to call them collectois niomim. workets and management alike At the othet end of the samplers While nvattv of the devices ate collectois spec 11 uni ha s been the 11 a in mg of i nd i v idua Is high] v specia Ii/ed m the control ol specific ha/atds. ospecullv those require the application of subsequent a na I v t ica I pi ta ed iih others provide foi a more ducet measurement of t\r ' 1 involving noise a nd t o \ it a i r coma mi na ms I hese dev elop- dose" Then basic appeal, howevei. is sirnpiniiv ot n mem s ate vv elc min'd bcea Use t hey corn rib ute stg mf ica m lv tvi the ultimate goal ol piotecting the health of workers bv providing safer and mote healthful workplaces 1 heoiet icallv ela hot ate ea libt at ion pi oeedut c s a t e uni . . sarv. and all that tv needed is a lanlv tellable mile pi measure e ypostite diiiation 1 bet e is some i et'oemi m: : At the same time, ptofessional industrial hvgicmsts teeogrn/e that often the ethical step in the process is not recog union of toxicity. but evaluation of ha7ard which leads to the subsequent development of the most effective means of tempeiature and humiditv tnav affect the obseivat' therefore, most man it fact utet s ad v tse the user t o t epot i ; h environmental conditions to the analytical lahtuuioiv r" cessing the dostmetet com rol w here w at ra med 1 his hey step of ev aluat ion is I he unique domain of the industrial hvgicmst. often supple mented bv other members ol the occupational health and sal el v tea m, W he t e ev aluat ion tcquit cs t he determination of w oi ker exposure to an borne to sic substances, the industrial h \ g'cnist has seen a revolution in t he dev el op mem of sophis ticated techniques and equipment Rather than v icw mg passtv e dosimeters as a not her w a replace the tndustual hygienist, industrial hygienists nn recognise and appreciate the potential of the dosimcn ihelping to achieve the hvgiemsts' goals That potential significant in that peisonal cfosimeteis. if pmpctlv to oflet the oppottumtv to tev oltmoni/c the evaluation m. 1 he parallels w tth detector tubes, as well as w ith muse ,n 1 he "oipan-grinder" tmpmgcr sampler is a relic, having been replaced hv constant flow, eight-hour battery-operated pumps, light enough to he carried bv the w orher. The liquid bubbler and impinger have been replaced bv the charcoal and chemical substiate sampling tube. The laboratory has come to the field in the form of the portable gas chromato graph and infrared monitor, albeit with a price rise directk proportional to the sophistication of the equipment Even the once lowly. direct-reading detector tube has become legitimate with the establishment of government programs to certifv accuracy and precision, Bui while most evaluation techniques were reaching the point w here ihe industrial hv giene staff required the addition ionmng radiation dosimeters, are obvious Indeed tl parallel with radiation dosimeters, espectallv film badges Striking. The opportunitv to significanilv expand the me surement of worker exposure to nianv toxic material'- e. proxide a quantum leap in oui ability to provide sale .o healthful workplaces With anv sampling device', hout u there also must be the understanding t hat use ol sue h dev n is only one part of the evaluation step 1 he concept' proper selection of workers at risk the undet standing limitations, inlerferences and similar factors and ultima!' the proper interpretation of the results ate 'till kev mp dtents in the evaluation step 1 he possibility ol "lalse m i tivc" decisions leading to erroneous assumptions ot sate: or "false positive" conclusions leading to unwattani of someone with a Ph D. in electrical engineering, a new expend it ures of resources lot com i oh still exist't cg.u tl '< device has appeared which has the kev of smtphcitv - the of the measniement device used fopv'iQ*' 196^ Artvfricar fnduStOA1 Hvq.rn* Ajoy .......... Ar'-1 ran lnOuMi.il1 Hvp*(>f^` Assn; elm" JOURNAl <41, h 8? 3M 107251 With the rapid proliferation of passive dosimeters in the past se\ era I years, it is appropriate that industrial hygienists evaluate the "state-of-the-art"and. as professionals, become involved with the proper application of these monitor ing dev ices theories of operation In that passive dosimeters by definition do not use an air mov inp dev ice to transport contaminated air to a collector, nat ura I lotces arc relied upon to ensure that a rcprcscntativ e amount of contaminant is "seen" by the detector. T o date, one ol two principles has been applied m the design ol dosimeters 1 he litsl. and most vv idelv used, is the principle of ih/lu\ion ol contaminant molecules thiough a stagnant pas (air) layer I he second principle mv olv es the ahsorpi ion in and subsequent /in;nu'unon ol contaminant molecules through a membrane Dithi\innal monitors relv on the movement ol contami nant molecules acioss a concent rat ion gradient wlueli lot steadv-state conditions can be defined hv l ick's f irst 1 aw ol I >il I tision 11' dc W - -DA-- d\ ft I where \\ ~ masstianslei late, ng see. I) -- dilliision coellicicnt. cm' see. A ~ 11 oss sect lona I area ol dill usion pat h. ent'. a rut dc ds - the instantaneous rate ol change in cone cm i a non over ddfusion path, (ng cm'1 lent 1 Considering the change in concentration (Ci -- (',,) ov i : ihe total dilliision path length (Xt -- X. = --I ), cquatioi I I) becomes w ^ n y tc, - c,,i (2i where 1 - length ol the dillusion (static) path. cm. ( i = ambient concentration of contaminant ng entand C = concentration ot contaminant at collecting suiI'aee, ng cm'1 If an efleetive collection medium is employed, the contammart! concentration at ihe surface ot the collector (Co) can be as* mired to he zero, and multiple inp both sides of equation (Z I hv time, y iclds M = P ^ (Ci) t (3) where M = total mass transferied. ng. and t = time that the badge ts exposed to the contami nated aii. sec. It is also interesting to notethat the units of the product of Hand A divided by l.are cm* see. vv hich are the same units associated with active aii-moving devices such as personal sampling pumps Rearranging equation (?) as follows MI C` = DAt it becomes apparent that tiv e 1 actors a I feet t he measure men', of the ambient air concent rat ion ol a substance (C i) 1 wo ol the factors (I and A) arc physical parameters associated w ith the construction ot the dosintelci. one ( M ) is prov ;dt d hv measuring the total mass of contaminant collected b\ tfu sampler, another is the duration (i) the sampler was exposed to the contaminated atmosphere, and the tinal (actor (l)i o an individual property of each vapor or gas It also o known"' that the diftusion coefficient is ditectlv propo> t lima I to Ihe absolute temperature (I ) ol the v upor. raised i, ihtee-halv es pow er a ltd mv ei sclv pi oport mnal to the at nto spheric piessure (P|. Dosimeters that iel\ on the ptinciplc of pirnwaiinn through;! membrane are especially usef ul w here t he com am inani of concern is usually found mixed with oilui inteileiing vapors or gases or when a liquid collecting medium is emplovcd T he goal then becomes to identity a membrane material that is highly permeable to the contaminant ot interest and impvrmeahlc to most cither components in He at mosphcrc, and ot the collecting media Ihe determination o( ambient concentrations of a con tannna nt using a per meal ion dev ice can be determ med turn the toi mu la (' = wk t (6) vv here. 0 " concentration of contaminant, ppm w = mass ot contaminant collected, gig. k - permeation constant, ppm-hours gig. and t - exposure time, hours The permeation constant (k) is determined experimentally and is a function of the specific membrane material and contaminant ot interest sources of measurement error The most obv ioiis sources of error fot both ty pes of passive dosimeters arc appatent from equations (4) and (6). Com mon to both badges are determinations of the mass of con taminant collected and the time of exposure of the dosimeter to the contaminated atmosphere. For the diffusional moni tor. accurate knowledge of the physical parameters asso ciated with badge construction (length and cross-sectional area) and the diffusion coefficient of the contaminant are important. There arc at least nine prediction methods for calculating the diffusion coefficient, and in one study com paring observed and expccicd values for more than 100 compounds it was not uncommon to have less than 50 percent of the calculated results within + 5 percent ol the observ ed,1'1' Montalv o has described a procedure for limiting errors associated w ith computed diflusion coefficients.'4 At tot Am InC Hyf Assoc 1(43) Auftis* 19&. 3M 107252 It ast one ma nufact urcr, the 3 M Com pans, makes avatlablc its pi <Kcdurcs lm deter mining sa ntpling rates ( DA l ) lor its b. i dees 111 Its a ppi oaeh has been lo expet i men talk deier mine the sampling tale loi live or six compounds in a chemical famik in establish ihe iclalionship between the ddlusion coef t iclent a rid i he measured sampling rales Sa m pi mg rates lor oilier compounds are determined Irom the ddlusion eoellicienis calculated bv ihe Hirschlelder equation and the empirical i elat mnships de \ eloped fi om the test compounds 1 he lattonale foi the selection ol the Hirschlelder equation is not fmn but in the siudv ol the nine diffusion coellieient loimuias. the aulhoi concluded that lor highci molecular w - i a lit compounds the H it sehleldei, Hia td and Spa 1/ eq ua toms ucii in closest agteemem with deteimmed values"' I in l lie pc i me a l ion in on not. ace male deter rmnal ton o! t hr pcimealton coellieient lor each monitor is ncccssaiv lor oh'ummg accurate tesulls Factors influencing petmeation include l luck ness a ltd u mfoi mil v ol the mem hi a tie, a 11 inn v ol i he mem hi a ne I oi t he a n,i k ic. sw el line oi shiinkage of the memhiaiic and possible cubing bv coriocnc1 chemicals I In pi o tile ills assoc ui led with a ecu I ate d el e I m I na t ions ()| tin in.is- ol the cunl.iminanl collected ate smiilat lo those i u i1 i' i d w 11 h ol lie t c ol Ic el ion dcv ice s such as cha r c oa I or `dua e c I tube's oi to those in which the collection o1 ihe c on ta m m,mi; in \ ok c's a ehermca I read ion with t he col h , turn medium I sine known amounts or concentrations (p , . u lurmnunts t" detiimme collection and or desorptnu re iic'i,"' is ,i' < i it ica I .i ste p lor passu e dosimeters as :1 1 t other methods ol collection Salination of the soil w ell as i In mi hscquem ae cu i tic > of a na k l tea I leeh n m , al'o pail of the t ot a I e 11 oi associated w it h 1 he mc.isu i Ant'thei common concern m till t\pes of environ; me asm emenls is the potential foi inter lerences, cilia p too or ncgati v c. from other c on la m mants in t he sa m pi; a .. As the evaluation ol passive dosimeters has maimed, i ik r c'ased a l tent ion is he mg pa id to possible interlei e nu s in mull i-e eintammant exposure situations in both the lahoia toi\ and held In evaluating such mlerletcnces it should fie iccogni/cd that there are several potential sites for such inter fercncc's to appear. eg.. cflects on adsorption or absoiption cffioc'iiCN ol the stimplmit medium chemical i eaet ions of t w o or moi e contaminants prior to ana k sis. and the multitude of interferences associated with anaksis of complex mixtures of gases arid ot vapors These problems also arc found in the mote classical sampling and analyti cal methods Accurate measurement ol the time the sampling device is exposed is essential to most industrial hvgiene sampling procedutes for both short-term and full-shift exposure measurements, ertots less than one percent, i.e 9 seconds in 13 mi nines a nd 4 8 minutes over 8 hours, arc not unreasonablc goals F or the diffusion coefficient and possibk the permeation constant.it w ould appear that three factors have the greatest effect on vaiiabihtv These lactorsarc the twoabeadv identi fied. temperature and ptessure, and. less readilv apparent, the velocitv of the air external to the badees Amf-fn <ir Indukthd HvpfftH A'Id!i0f lOU^NM i43i e Considering lempeialme and ptessure, and iclcrrinp to equation (5) it can be show n that a tempi iat uic r isc Mom ^ to .35 C would give a lb percent inctcuse in the diflusum coefficient, while a rise in hatometm pusum Mom 710 to 8 10 m m Hg would Cause a 14 peticnt decrease "Howevei at the same tune, the changes in lempeiatuie and pressure also a re affect ing t he c on cent ra t ion ( mass volume act ua Ik densitv is the proper term hut most authors usi concemia tion) of the contaminant in that concentration is mveisclv proporl lonal to the temper at u i e and d u cctk pi op ml lonal to the ptessure As a result the total mass ( M ) c olleclid h\ tin dosimeter is onk slight k af leeled bv temper a Hi r e ( M '* I I a nd is rude pc'nde nt of I he pi ess u r c '1 ( oti sc q tic r it I v with a 1 ambient tempc rat cues t lie d il I usion coel I n lent will ru ho, ahcvtrt 0 5 percent per T .and the totaI mun collecred to 11 sa mplei will increase less th.r n 0 3 pen. o il t pci ( 1 he u I or, a temper at urc cha nge I mm 25 to 7(1' < it II m or I ci n (I m' introduce a measurement eruu ol less than one p, inn' while a change from 5 to 7s; `C it uncoriieted would ml r oci uc e a n ci r or of a hour live pel oi n l I he f i na I m ui i c c of c 11 r u t o v on s id e t i - 1 he v c 11 u I! \ o! lii an e xtei rial lo the dosimeter ol n n this n n lei i ed to us | ,K . vclocilv In an carlv asscssim nl ol l.n, i sckisirx cllc'cl-. i ; era 11,v t fie lack l hei col I ompk i ns and < olds mil h point o that the rm porta ill consider at mri is to contain all resist, me to contamma nt tta ns port within the Magna in an la v er ms id, the device 1,1 As Jonas <*/ a/ suhsequentlv noted tfn l.n v eloc it v du ect k af I eel s t he i om ; nt i a lion gi ad n. m t < 1 equation (2), and (. can no bulge t I'h assumed to hi in ambient concent r a I ion w hen the an e x tei na I to llu bade stagnant 161 With /cr o or low laee v e101 11 ics the lengt h 11 1 "' the diffusion pathwav is efleemek extended, and then a a dec tea se m the measured ambient concentration In J ompk ms' a nd Goldsmith's work w it h the (1 AS Fi M )(> I thev determined expenmcnlallv that as long as lace veloii ties weie gieaier than 7 5 cm sec (15 Iprn) there1 vvas "m. significant el It'd on dosimeter lesponse "howevei expeo mental results supporting tflis ccmclusion weic not pn sented 111 High face v eloc 11 it's ma; a ko af I ect t he cone em 1.1 non gradient C'ommcrcialk available ddlusion rievno iek on either a la rge rat 10 of diffusion pa 1 h lend h to d il 11 sion lube diametet or a wind sttecn to limit ermis Mum this condition. One of the most comprehensiv e tests to doc umeni soui c e of error has been cond ucled under eont ract I or 1 he Nat mi 1.11 Institute for Occupational Safetv and Health and although concluded, it is not vet available as a public report 1 In studv involved evaluation of the GASFiMHi! and kl Organic Vapor MonitorTM (the DuPont badge not heme available at the time the studv was initiated I via ihallcngc with several organic vapors The factors m\cstig.ued win precision, effects of storage, maximum and minimum levelof quantification, face v el 001 v elicits C Men 1 s ol ti m pel a 1 in and humidilv. ofl-ga"ing (related to 'toiagi 1 exposuii in mixtures, problems associated with applicable anakine. methods, and adsorption c'l the i onta in ma nt bv the hadg< itself with subsequent leaching lo tin sensing surface' I h possibilitv ol adsorption hv tin badge bock thus givim. 3H 107253 higher results if the contaminant is subsequently released to he acme medium, is of special concern in using passive !<i-imctcis to measuie very low ambient concentrations 'iii h as might he found in air pollution studies. Such interest and loncetn are evidenced by research on the subject being sponsored b\ the US. Environmental Protection Agency I I' A i lh` because of the lowei concentrations involved with n pollution siudics as opposed to workplace en\ironments. n I I'A Ko is concerned with the background or post- o . c ontaminalion le\els associated w ith the sens- r, d , Initially . the focus concerns organics and acti- .( .1 , : sii os although numerous factors mat affect the uon ol concentration, only face velocity and the 11 of I he dil Iusiori coefficient are unique sources o [i.issue collectors Therefore, if face velocities i " i iii to present "siar\ation"(probabl> greater than -oid it diffusion coefficients have been accurately i xperimentally determined, passive dosimeters ' ; i suits comparable to those obtained w ith tradi i ' sampling systems statistical considerations II i ',1'mi' ,i n\ new monitoring met hod. extensive la bora o' and held testing is necessary. Interpretation of the ill - i d i Ir se tests requires the application of appropriate i..: - ' i i ii i. h tuques 1 he use of statistical techniques w hicfi n t a n i ugl ul a nd easily understood is important, const nii'inh a discussion of the techniques used to evaluate passu c di'simeters is appropriate 1 hen are numerous statistical tests which can be applied 0 both field and laboratory validation data The main difer cnee hot w ecn the two situalions is the degree of certainty >1 the "Hue" concentration of the monitored envnonmerit 1 n the field the true value is usuallv an estimate based on the esuits of a standard sampling and analy tical method In the a bora lory ex pen mental " know n" concent rations are ev olv ed and are then used for comparison with the concentrations estimated from sampling and analytical methods What is often not siatcd is that a certain amount of error also cxisis in rhe determination of laboratory -cv o|\ed `known" concentrations. These errors a re often difficult to estimate. The "known"concentration is often calculated by weighing a sy ringe before and after an injection period (mass alanre) or stmplv by injecting or allowing to diffuse a ncasured volume It is assumed that the aliquot delivered vaporized or diffused into a lest chamber of known size, ssihlc sources of error include adsorption to or leaks from Tic >est chamber, absorption and adsorption to articles placed in the chamber, degradation of the analyte by air oxidation or hydrolysis at high relative humidities, and error in measuring the injected contaminant. A backup monitor ing system may be used to ensure close proximity to the known concent i at ion For example, an inf i a-red (1R) anayzei oi gas chromatograph may be used as a check on a known" concentration In other instances an IR analyzer or a direct reading instrument may be the only method fordeterntinmg "know n" concentrations. In this case the error in the instrument can be calculated or estimated Charcoal tubes and critical ori fices also have been used to measure "known" concentra tions, II error in both the "known" concentration and the estimated concentration arc considered, statistical tests used to validate the experimental method become considerably more complicated, hence, the error m measuring the "know n" concentration is usually assumed to be small and unimpotlant.'9' Methods described above for determ mint the "k nown" concentration vary in their accuracy, a fact v,inch should be considered when evaluating validation data for any sam pling and analytical method When one is validating a method in the laboratory. there atciwomain considerations thevariationofthesamplesoi data points about their mean, and (he dev lation of the sam pie mean from the true mean or "know n"concentration 1 he first consideration often is called precision and is piobablv the most important and reliable measure as it doo not depend on the error in determining the "k now n" concent ra tion Piecision is estimated by determining the coeffu lent ol variation (('V) or relative standaid dev lation of the data set as follows CV = \ y 100 (7> where: s = Standaid deviation of sample data set. and X -- Mean ot sample data set Where samples are taken at several concentrations, it is neeessarv to determine a pooled coefficient of variation which involves determination of number ot levels tested 111 It should be noted that determining the number ol concen trations (or more appropriately, the number of statistical levels) is not always straightforward. For example, if 10 samples are taken at each of three concentrations, and if within each concentration five of the samples are collected over four hours w hile the other fiv e arc collected over eight hours, art there thiec levels or six levels'' The important point to consider is whether rhe differentiation of a level is based upon an anticipated difference in the sample mean Certainly il the investigator designs the experiment with different lime levels, there is an anticipated effect of time on the mean. Unfortunately . when experiments are so designed, statistical analyses at the various levels usually are not performed The second star istical consideration, the difference between the sample mean and the "known" value, is sometimes called accuracy, but the term bias is more appropriate. It is defined as v_Y h = ----- X 100 X(i (8) where X -- mean of sample data set. and X(i = "known" value at level rested If more than one level is sampled, it is necessary to deter mine the pooled bias of the data set."1' .08 Am tnd Assoc J (A3 Aupusl 19ET 3M 107254 I fu blits (or a given set of data can sometimes be cor rected If the average bias (either the average of several samples at one level or the pooled bias for several levels) is laige one should note if the components of the bias value (citlu i the indn idual samples or the levels) are consistently ntgaiive or positive. If the bias is large and vanes consts11 n11 v in one direction, the precision nevertheless may be oil; small I n t his case a physica I or c he mica I \ a riable may In V i insistently affecting the method (a systematic as opposed i i.mdom error), causing the experimental values to consi '' \ la II short or long of the "know n" concent rat ion 1 his ! "I bias should be corrected I ' Id it ion to i hese stat i si ical tests, others hav e been used 1 s the validity of passive monitonng systems Overall meutacy1 has been defined as (2 X CV) -I absolute ' a pi essed as a percent Others"'1'hav e used the pcrcent- ihc "known" concentiation accounted lor hy the : mean.! t w o standat d dev lations as w ell as t he let m ' ".atii etior1 M) which is equivalent to overall system ` \ Relative standard deviation has also been used. .1 d i ned as i he equiv a lent of C V " '' Add it lonall v. some '' a report only raw data while otheis report means V' ! t standard deviations or sample sizes, and various 1 'ii i omhmanons While all of these statistical deieiminai1 "i have utility, it seems important for comparative purposi s i o consistently use those determinations w hie h giv e the rnosi information in the simplest form Certainly, bias and piciision meet these criteria Oise usston ol one other point seems necessary NI OS H "" has ptoposed as a guideline for then own internal pui poses that sampling and analytical ntcihods meet a minimum tequiiement ol i. 25 percent accuracy, that is, the absolute total error of the method should be less than 25 percent iri at least 95 percent of the sample population (assuming a nor mal distribution) MOSH derives the maximum precision value for an unbiased method given the accuracv criteria stated This value ( 12.k> percent) is the ma\imum precision value acceptable for an unbiased method Although the 25 percent accuiaev criterion has been criticized hy some authors,11,1 it was adopted lot MOSH's ow n internal use and is not meant as public policy However. OSHA adopted the same c rite i ion for the benzene si a ndard w it houl a complete derivation or explanation. Consequentlv. this criterion has been crit)ci7ed and alternatives have been proposed."1' A second important point is that bias is also considered in Ihe 1 25 percent criterion according to a somewhat complex statistical relationship,"01 bui the overall svstem accuracv as defined earlier"1' tsa fail approximation if ihe method haxa true bias. i.e.. ns mean is statistically different from the "know n concentration." A final point is that as the number of samples at a level increases, the standard dev iation and CV should decrease These considerations are important w hen evaluating passive monitor validation data, espcciallv in those cases where manufacluters have stated that thev have met the 25 percent accuracy ctiterion. For field comparisons of conventional and passive moni tors. different statistical tests are necessarv If passive moni tor values, for example, arc plotted against chatcoal tube AfTitfir^t induM.'ii1 HyfMgpp A<.sottattoo iOURNM itt) S S? results (Y vs. X) and mote than om concentration o sampled, one would expect an inircav in X to cause at increase in Y. tf the increase is hnejr, and the sample value1lie on the regression line, ihe corielai ion oi fficient (r) w on Id have a value of one. If a change in X hi mgs aboul ari equal change in Y. then the slope w ould a Iso hav c a va lue of one II the indiv id ual values 1 or the i w o dev ices a re indeed eq u i v a lent, the line should intercept the origin 1 a eh of these 11 la tionships is expected within reason The difference of ihe slop from one, the correlation coefficient fiom one, and the intercept from 7eto can and should he tested In order to perform the regression analvsis desiiihed above we must assume that X (active sampling data ) is not subtecl to error Of course, vv e know a nil ea n ca k ulaie undo laboratory conditions the enot ol avtivi sampling svsk m-. There are at least thiec reasons win tins ernu n olien overlooked First, it is assumed that consideration of tin erroi in X would only cause small cldleiemes in legiession analv sis results Second m add n ion t o lahoi at or v duimi strated cri or, a mngc ol cm or s int i odneed by va i v mg cm i ronmental conditions must he considi ied While diltu nil io assess, these errots niav have a profound etfert on X ami indeed the ciror in the X measuieiium may hi as gu.-.i oi greater than that foi Y Finallv, if the eiioi in X is in fu considered the statistical tests aie com pie x Such tests have been discussed (or biological pt oh I e ms 11 howev ei. the t heones apparently have not been applied to sampling and analytical methods even though then appropriateness has been recognized 1 applications From a historical vantage, one ol ihe earliest reports ot a "passiv c" monitor for evaluation of an borne i nnta rnmn m s was patented by Gordon arid I owe in 1927 1-11 Then gas detector for carbon monoxide iro olv ed an "easily frangible vessel containing a solution of salts including palladium chloride, and a covering for said vessel of a light colored absorbent material " The principle involved breaking the vessel (a small ampule) and noting the subsequent lolot change of the solution as n reacted w uh the carbon monox ide on the light colored absorbent matenal This ivpc of semiquantilativc dev ice was certainly a fotetunnei ol those that are available today. though it was undoubtedly aflcetcd by air velocity as a stagnant air laver was not empkned An extension of Gordon and I owe's concepts in the late I9h0's provided the basis for Plant7 cl at to develop a personal dosimeter for measuring hv d ra/me. unsy mmet rical dimelhy Ihydraztne and mo no met hy Ihv di azi ne 1' T he reac tion of these compounds with a "colorimetric substance" (bindone) produced a purple color, the intensity of which was dependent on both concentration and duration of expo sure. Color standards then were used to est i mate t he conceit (ration as a function of the 11me the hadge w as exposed to t he contaminated air. consequently. the method was only semi quantitative. In considering sources ol cnor the authors noted that the purple color would also he produced hy all volatile bases that weie tested, including arnmoma ahphatic amines, aniline and cigarette smoke 3M 107255 } Ol miriest in ibis rewcn, however, arc quantitative drurci based on the principle of either gas or vapor diff uvion i>[ peimcation through a stagnant air layer The firsr such dev nr to he reported in the literature was described by I'd lines a nd Gunnison in 197 7 T heir dev ice employed the pi me ipie of gas dilfusion to determine airborne concentrations of suifurdioxideand will receive further consideration suhserpn nt i v I o ga in t he best ov erv lew of the v a nous a pphc.iMons cl if eve concepts, it is probably best to proceed b\ considering first the inorganic and then organic gases a lid \ ,1 pcis inorganic gases and vapors ammon/a In |4"'f' Ma/ur rt at described the use of the Abeor GASHADGf to sample employee exposure to ammonia (i hi, lev k e i in tenth is not mat keted) "*' The m\estigatois n pl,u ed thee ha i coal pad normally lound in the G ASHA OG f will' an .Rid impregnated ahsotplion pad Of three acids r i si ed ph osplroi ie w :rs most success! ul tn prov iding the best a ppi c v imaiion ol theoretical concentrations I hev detertnimii I), iw ev ei. that \ o la t ile amines, specifics llv cv clohexv Iieiii'ir ouId prod uee high r cad ings. as high as IX5 percent o. tin `.ntheiic atmosphere This led them to replace the g lass fihr j d i a 11 shield on the fi ont ol the G AS B MX! F w it h a `ilia1 o.iI impiegnated glass fiber filler which had been join..' 1 vi ii!, a k oholit KO11 containing 0 I percent stir la. lam I ne ; haicoal served to adsorb amines as thev dif fused nun t lie dosimetet while the KOH (aided hv the till":' a n:: i I mu na led n i ev ei si hie a mrnonia adsm pi mn hv i he t ha11 oal, w hich w ould hav e caused underestimation ol tin ambient ooiuentiation Additional labotatory cxpciirnenfs (iemonsttated that storage time of up to 47 days pi mi t o a nalv sis. did not appear to ad v ersclv affect the results Mine reientlv. Dul'ont has developed a commercially .nailable svstem for the measutement ol several airborne i in,tamm.ini- including ammonia In 19X1. Krmg el al Jeset itn d I )u I'ont\ PRO- I E k'* sv stent for ammonia nitro gen d in v ide a nd sulf yt dioxide sa mpling a nalv ms using ;t colorinietrii readout msti tintent T he ammonia badge tdies on mole tula i dift usiott ol ammonia and subsequent chemical t:-;rnon w it h a solution of 0.7\ boric acid and 0 03N sodium potassium tartaratc (\t< ) After exposure, the reagent pack is removed from the badge holder and analysis is initiated by f re sMng reagent ''blisters" w hich arc adjacent to the absorb ing solution This action causes the release of a modified `ses,let's reagent and the subsequent development of a , i ed solution hot a mrnonia. mavimum colot intensity is dev. loped at 42? nanometets. The absorbance of the sample is then compared against a standard curve based on Beer's I aw After deti rmmalion ol the precision of the analytical method and venluation of the Imeai langc of the coloi c he m i si i \. la hot at oi v testing was conduct .1 to establish t he opi ' ..tional range as well a- precision and accuracy of the ov t . ..fi nn ihod t see T ahk I) "1 lie miniimum and maximum lime of tin- sampling range were found to be 50 and 500 ppn, bouts, r espee I iv elv Tor art eight-bout time weighted ,1'ri.ijr T. so .allies eor iespvind to oi i -lourlh and iwo and one-ha If times r he current ACGI H I hreshold I mm \ alue ol 25 parts per million.In considering sources of error, environmental effects including temperatinc (10 to 40 C). rclat iv e hunndit v (10 to SO pei cent). pressm e (770 ro 790 m m Hp). and face velocity (2 5 to I 25 cm sec) wete inc luded Ol the environmental factors evaluated, temperature and the coneentration of the contaminant were identified as being responsible lot 9K pen ent ol the data v a t tat ion f oi ammo ma. a temperature cot tc cl inn fact or. of 0 h per i cm p- r oc gt cc ccntigiadc was suggested Aha imtsmsitiii ww-.ti,_ .i.uaec stability of both unexposed and exposed hadges Result-indicated that t cf ripe rated sum age is net ess.u v to e x tend r he shell life oI unc xposed badges One e t he badge is e x posed to am mom.i and hr I in c the t eagertts ate mi xed the badge c can he slot ed I <u one (mum lempetat cue ) t o t hr ec (11 11 iget a Ic'd I weeks without losing anv ahsoi bed i ontanunant Otu i the reagents ti i e nil xed a nil coloi I or mat ion o si a i ted the badge should he lead w iihin W minutes Add u 11 .n.,1 11 i u1 i <i!<condueied hv |)u!`ont an slimui <r I ahk I carbon monoxide Sti oi and Anders of the 7 M ( on i pa to have din: i>i d i ,. 7 M ``dneel-lead ddlttsional monitor" to: evaluation o' exposures to carbon monoxide* '' 1 he piitnipir ini eko tfre reaction ol the c.uhon monoxide and an untepot teii teapentfx) to got a vi-iblr coloi ihan-'r (mn pm! ;o i.m 1 licot et tea !i\ 'if a nv pint coloi IS Iiin I V a dk a it U no o theexposun period t he n t he c X pin u i vc a- 'ess h.o or time w etghted-av i I age ol 40(1 ppm limit - ' I In v also i.vi that not mg I he 11 me t o t he end pin nr a II nw . I o; , a I, : 'a i n >n 4 the avetagi eami c nt t at ion ol catbon monoxide dunng ike exposure penod The aulhots present vummsrv result-, ol la ho rat or v evaluations using an infra t ed i a dial ion dev iCi to establish "know n" coneentiations (see lable I) chlorine Haidv el al have desc-ribed a persona! chlorine monitor ( R f A1 . Inc.) w Inch emplov s rhe pr me i pie of per meat ion oi the gaseous contaminant thiough a silicone membrane and into 10 ml ol a fluorescein-hiomtdc solution,1'1'1 f'olortmet ric techniques 1 hen can be applied to detetmine the chlorine concentration T he authors report a detection limit of 0 01 7 ppm chlorine for an eight-hour exposure, with a "working range" of 0,1 to 2.0 ppm, "1 hev also suggest that for shorter time pci iods. concentrations of up to fivc ppm can be deter mined Other observations included effects of temperature, humidity. absorbent concentration. pH and response time, with all laboratory results presented graphically Motcculon Research Corporation has recently introduced a chlorine monitoring device which relies on plastic film impregnated with liquid reagents,1^1 F.xposuie of the badge to chlonne gas gi \es a v isiblc, "blue-purple," color change OpticaI transmission measurements, and comparison with a st and a ul cm v e. i a n then ptov ide quantilati v e exposure-, in ppm-houts The manufacturers summarv results indicating effects of lempcralurc. humidity. vv ind velocitv and concen tration arc reported as pi esent mg an err oi at the 95 peri ent confidence level, which is "less than d 15 percent" e in An- /no Htf J (43' AuCu'! 19?? 3M 107256 Chemical TABLE I Inorganic Gases and Vapors Laboratory Results Dosimeter* Bias'* Precision' Range" (ppm) Reference Notes Ammonia Nitrogen Dioxide Sulfur Dioxide Hydrogen Sulfide Mercury CO DP DP GB GB DP OP MDA GB DP DP GB 3M 3M 3M 05 05 -3 2 -32 -0 9 -4 9 -1 -0 8 05 17 03 74 69 93 21 7 75 87 41 13 8 58 75 15 3 9 2 47 20 50 20-48 6 62 4-1 1 4-11 4-11 6-9 4 6-5 3 411 4 11 16 22 0 03 0 3mg/m` 0 05-0 2mg/m 50 1830 24 26 23 1 38 ` 24 36 1 38 24 1 32 33 27 t r, HI G M1 H1 1 1G (, *DP-DuPont ProTek Colorimetric System Badges 3M-3M Company Monitor, MDA-MDA Scientific, GB-Abcor GASBADGE "See text, equation (8) ' See text equation (7) "Some values are rounded to nearest whole number 1 Bias consistently negative "Results derived from Table III of McCammon et at`': ` Results calculated from data provided in reference "This product is not currently marketed `Bias could not be calculated from data given hydrogen sulfide In 1977. lompkins and Goldsmith described the developmcnt of the GASBADGE personal sampler1" Although later ssork with this de\ice focused on the collection of organics on an actuated charcoal substrate, initial studies tescarched sampling of both organic and inorganic com pounds (The GASBADGE for organic sapors is now mar keted by National Mine Safety Company. and those for inorganic sapors are not currently marketed ) Applications inv olv ing inorganic gases relied on collects e elements of an "appi opriate substrate impregnated vs ith a chemical medium specific fot the contaminant of interest." Based on 60 obser\ations. the authors' statistical summary is presented in Table I Eighty percent of the measurements were within 25 percent of the "true" value. Challenge concentrations were established in a "well-mixed" environmental test chamber and were measured with an "independent wetchemistry sampling tram." Hardy and associates have described a permeation device ( R E A L, Inc ) w hich relies on the permeation of HyS through a dirnethv I silicone membrane and subsequent reaction with a solution of 0.2N sodium hydroxide and EDTA.'301 The colored product (methylene blue) is measured spectrophotomeirically and compared with a calibration curve to determine ppm-hours A knowledge of exposure time then allows for the determination of average exposure over the measurement period The authors note that a critical step in AfTtencdfi InduMfirf! Hyfupnp A\mk idtion JOURNAL (43} 8 SP the development of such a device is the experimental deter mination of the permeation constant (see Equation 6). w fm. h inv olves calibration of each monitor bv exposurc to known concentrations of the contaminant. The results of this labo ratory research demonstrated a detection limit of 0 01 ppm foraneighi-hourexposure.withaworkingrangeolO I to 20 ppm and a linear response up to 200 ppm "Ihc working range corresponds to one one-hundredth to two lime-, the currenl eight-hour TLV of 10 ppm l2>' Evaluations ol en\ ironmentai effects indicated that neither temperature over the range of --3 to 39 C. nor humidity. front 0 to 99 pereeni relative, caused any significant variations in response of the device Further research demonstrated a good response to high concentrations in less than one minute, adequate sam ple st a bill ty up to 10 days if EDT A is used in the absorbing solution, and negative and positive interlerences. respec tively, from chlorine gas and nitrogen dioxide. Precision and bias were not reported Anotherapproaeh for thedciermination ol gaseous hydro gen sulfide has been reported by Graedel and 1 ranev ,!" Their research inxolved using a scmiquantitative method withoutastag na ntairlaverand re lymgonthe disco lo rati on of lead-stabilized polvv iny 1 chloride ( P\ C) The technique tnvolxes the diffusion of gas in a polymer and. at high EES levels, the detection rather than the measurement of toxiclev els of EES. Screening applications lot low lev cl exposures also are discussed 3M 107257 hi mercury In 1977. McCammon and Woodfin of NIOSH teported the ir-nlts ol a laboratory c\aluation of 3M's mercury \apor momiot 1 The monitor's operating principle inv olvesmoleeul.ir diflusiort and deposition of mercury \apoi on a gold snhMraie The resulting cl . ngc in electrical conductivity across ihc gold toil is iclatcd to the amount of mercury ahsoihcd by th<_ toil Three other sampling methods, all of w Ins h in\ olved the active moiement of air, also were inves tigated and include the I.AST tandum sampling tube, the bi'pcaiite tube, and the iodine impregnated charcoal tube I t>: the passive monitor, precision and accuracy, the effects ol lace velocity and teinpcratute. and potential interferences yen invotig,ited Concentrations of meicurv vapor m an c v posm e s Ii,imhet vscie monitored u it It an ulira\ mlet met eurv i.ipoi meter, which in turn was calibrated by measttremertts using the I ASI method To determine precision of the monitors I 2 dev ices w etc exposed to a test at m os p lie re R< -till' ii-.m tliiee measuiements of the test atntospheie i * mg the 1 ASI method gave an "expected" concentration ol 0 OV- nulligianis of mercury per cubic metet of an (mg m i with .i standard deviation (SD) of 0 00? mg m* and a eoeflicient of variation (C\'l of 0 037, Precision and bias calculated (or the data given in Table III of McCammon rial' ' is summarized in Table I. A least squares regression a nn I v sis o! t he combined precision and accuracv results I or the passim- dosimeters versus ihc "known" concentrations i'a-c a Y miereepi of -0 004 mg m3 and a slope of 1 003 I ests tor tin- effects of face \clocitics from 25 to 1 25 cm see `id t(i 2.V) i pm ) did not appear to have any adv erse effet t on per ior nm n.. w bile va> lanon of temperature cxperitncntallv sonfnmed us effect on both the diffusion constant and the concentration of the contaminant The potential effects of changes m relative humidity were not discussed hv the authors The other area of investigation in this studv involved potential interferences of chlorine, sulfur dioxide. 0 nd hv di ogen sulfide Concomitant and sequential ex posm e in mcrcurv and chlorine, the latter at high levels (5 8 ppml. produced a negative bias, but a similar effect was observed with the l)Y meter and the I ASI svstem The authors suggested that the mcrcurv and chlorine may have been trading to form mercuric chloride which was not being measured hv anv of the systems The interference effects of sulfur dioxide and hy drogen sulfide, although less than chlo rine also were confirmed In 1980, McCammon and his NIOSH and OSHA coworkers conducted further tests of the four prevtouslv d- sf-ihed mercury vapor sampling and analytical methods lU' 1 tii design of ihis laboratory experiment involved intetcomparison of four methods, and the findings suggested that the variability of the iodine charcoal tube method is signifi cantly different from that of the other three methods. It was observed that the other three methods, including the 3M pass is c dosimeter, exhibited pood precision over the conccnIraiion range of 0 05 to 0 2 mg m3 as show n in Table I. Recently SKC. Inc., introduced a gas monitoring badge (prod need by G M D Inc ) w hich uses the principle of molec ular diflus-, >n (without a stagnant air l.rver) to collect met- cury vapor The sampling media is referred to as "Hydrar Sorbent."and "extensive"but unpublished field and labora tory testing are cited to show that "chloi me. moist ure, etc , do not interfere" with measurements HY DRAR is devel oped from a "manganese dioxide catalyst material similar to `Hopcalite.' " Quantitative determination is made hv chemical desorption of the mercury and analysis with atonm absorption nitrogen dioxide In 197h. Palmes el ol. rcpoi ted t he result' of then ev aluui ion of a personal sampler for nitrogen dioxide (NOz)13'" This work was an extension ol then earlier pioneering eflorts m developing a personal sampler, emplovinp the pimuplc of gas diffusion lor sulfur dioxide In their design the sum phng dev ice v. as a 1.3 cm (0 5 inches) acrv lie tube. 7,1 cm ( 2 K inches) long At the "closed "end of t he d if I usion pat h (i nbe I w ci e placed l hrec stainless steel gr ids c oated with 11 ,e' ha no la mi tie (T I A | T T A w as selev ted her a use I ) u ea n' ci - s N () ef fictent ly 2) it pi o\ ides a si able sam pc p - in !,u "id u il v telds a chemical tonipls'x w it h NO thu'is u" .'ci lime Subsequent anals sis y u'lderl a colot t o i nrupU \ w hose ahsruption was nieasuied at 540 rianoiiictci- Result- were then r om pa t ed aga in si a standard eurv i w In; h ohe v cd Bee: N law The expei imental evaluation ol the NO sampler involved ehanihcr measurements compared wuh "knov n" v a lues deter miner! hv ihc v ohmic of NO inaailm oJ ii ih1 i ham he i oi the w eight loss oi NO . ft om a p* Miie.ii i. m tohe Although neit bet indiv idti;il not sununa > v n i.li-y-o r ' sented. graphical comparison ol ifie data mdu at.,! a i h 1 agi cement bet w een the passi v e sample: t esuit s a ml t In oi i 11- cal e oneent rations I he effects of w irul v ehn it \ and direction as well as stahiluv orei 11me also were considered In deter - mining wind effects the uptake of water vapor, rather than N(),i, was measured, I he results indicated that there was an increase in average uptake with inrreased velocity and that the 45 degiee incident angle gave the highest uptake (135 peieent at 258 cm sec) Across all angles of exposure (0 to IK0 degrees) the average uptake mcicased Irom 2 to 14 percent as the wind velocity increased fr om 50 to 258 cm sec ( K)0 to 5 Ih fpm) Siabiliiv srudres indicated that the badges could be used for months botlt after preparation and before exposure as well as aftei exposure and before analysis In the prev lously described studies w ith the G ASBADGL. Tompkins and Goldsmith also monitored for nitrogen diox ide."' Their summarv results fot 82 observations showed accuracies and precisions as summarized m Table I ITiphtyfrv c percent of the observ at ions were within 25 percent of the "true" value A commercial model of the Palmes passive sampler has been marketed by MDA Scientific. Inc., and additional laboratory testing demonstrated a linear collection effi cient's for any given dose, i.r., concentration X time (see Table I)1**'1 The samplci exhibited a consistently negative bias as compared to concentration determinations using a continuous monitor and the NIOSH wet chemical method As noted earlier, the DuPont PRO- FF K sy stem includes a badge for nitrogen dioxide, l.aboratorv test results of this device arc shown in Table I 13,1 An, Inti Htc Assrv Ayj us; 19>T 3M 107258 sulfur dioxide Av noted prev tously. pioneering w ork in 1973 on the design of a sampling device which relics solely on diffusion of gaseous contaminants through a stagnant air layer is attrib uted to Palmes and Gunnison.1221 Their initial studies involved experimental work on different tube lengths. The collecting medium was a complex of mercuric chloride and the final analysis involved colorimetric determination. The studies demonstrated that, except for very short diffusion paths (tube lengths), the diffusion monitor satisfactorily duplicated the results obtained by both wet chemical and conduct m met tic measurements. Although this study did not go into the ramifications of environmental effects and interIciences. it should be recognized as an important step in developing a new industrial hygiene technology The last of the three inorganic gases looked at by 1 ompkinsand Goldsmith in their studies of theGASBADGE was sulfur dioxide 111 Summaiy data for 23 observations on this gas are included in Table I. One hundred pcicent of the observations were within i 25 percent of the "true'' values The results from DuPont's tests on their sulfur dioxide badge also are shown in Table l.<38' organic gases and vapors Most passive dosimeters designed to sample for organicgases and vapors use activated charcoal as the adsorbing medium. As we know from its extensive use in active sys tems, activated charcoal has an affinity for a wide range of organic compounds Consequently, the discussion on iInapplications of passive dosimeters for the measurement ol organic gases and vapors first will focus on devices uMng activated charcoal and then will tutn to specific organic-which rely on other collecting media Chemical TABLE II Organic Gases and Vapors Laboratory Results Dosimeter* Bias' Precisionr Range1' (ppm) Reference Notes Carbon Tetrachloride Toluene Formaldehyde Benrene Ethylene Oxide Halothane Enf lurane Acrylonitrile Hexane Vinyl Chloride Methyl Chloroform Trichloro ethyiene DPA DPA NMS DP DPB NMS NMS 3M 3M 3M NMS NMS R 3M DPA NMS 3M DPA NMS 04 03 -1 7 15 33 -4 1 18 -1 4 3 -2 8 0 03 -1.2 -0 2 -5 9 -106 24 -3 9 -6 9 "0 5 44 5 25 17 63 47 17 17 32 74 48 87 2 37 47 45 2 76 77 19 3 18 57 228 12-47 0 2 -4 2 3 24 08 54 13 13 5 300 0 5-20 0 5 20 0 7 19 10-37 1 5-14 160 840 160 840 15-65 20-200 20-200 15-67 10 \ 45 13 55 46 13 E J 1 ECJ 53 44 J 44 J 39 13 FJ 2 HJ 48 1 J 48 t I J 12 E J 48 1 J 48 E N 12 fJ a3M = 3M Company Organic Vapor Monitor, DPA and DPB = DuPont PRO-TEK G-AA and G-BB Organic Vapor Badges, NMS = National Mine Safety GASBADGE. R - Real. Inc MINIMONITOR, DP = DuPont PRO-TEK System Colorimetric Badges pSee text, equation (8) cSee text, equation (7) ''Some values are rounded to nearest whole number r"Sma!l sample sire fKnowns were calculated using charcoal tubes with critical orifices This could affect the bias measure ``Preliminary results "Permeation dosimeter `Bias consistently negative JResults calculated from data provided in reference Ani-tii an Industrial Htpipnp Association JOURNAL (t3) 8 `82 3M 107259 $13 > i tivated charcoal devices m nl March. 19X2. (here were 1 our manufacturers ol passive , .inictcr-, which rrlv on dilfusion and subsequent adsorpm on (o activ .tied charcoal National Mine Serv ice Com, ns ((. -\sliA I Ki l ), 2 M Company (Organic \ apoi Momil i'11 Mont Compans (PRO-TF-K. G-AA and G-RH ...mim \ .mioi Aii Monitoring Badge), and the Mini Salets c, : a Coinpins (Vaporgard Badge). I ii I o'1 (oinpkins and (ioldsrnuh described the 111 ^ t n mcmml passise dosimeter (or monitoring organic m " 1 I lie i i ASBADGF relied on molecular diffusion ol . i f. i ll-' the badge and subsequent adsorption onto : - .ii.si I'siiioa) The authors deseloped the theoretical i uii1 pics ol ihe nadee's operation, and discussed scnoi is os er'pi i dtart and pressure, lace velocity clfects, and .pono........ i, Pieliminars results showing the badge's sp b'Mi/cnc el In I acetate, meths I eths I ketone and . ; cl o m i; i'1 piesentcd and were described as "sers . . i M-. t ,i pc [ i) 0 o , ;i, s ca r. sds cistern reported results ot lat'oi atm i ! i,i 11! 1 ' me oi the G \ S BA (Ki F lor act > liuut i lie I In .nl; ot i.. < spostiie ol V) badges to knossn eoncentr.i "i 1 n . A1 l.ihi'niini i aie presented m Table II I he tesulis . -. 111 a s i epi .i hi I it s ot the GASBAlK.I t n i me a - u i :e ot ,! i s ion11rile oset the range ol 0 75 to 19 ppm I lie 1 .a e ' m is in e in the la ho rat ors w as not gts en hoss es ei M me , neeu n'-. did coser penods ol up to seseti boms 1 ' pm.iuit' and relatise humidits tang;, wee. 'oil , i o , analssis to dctcinnne the elicits ol iIicm mt piesentcd Silseistem also looled ai oi c! [o , :: i ie in ies a nd del ei mined that the best i e mils l petic.nl) ueie obtained with lour ml. ot two percent ctone m carbon disultide. In 19D;, Bamberger t'l al conducted a senes ot iwhorutoi s st> t o es a lua'e the GAS BADG F IJ' Their appi oach ms ols ed e genet ation ol knossn concentrations ol solsents anil .h -1 ei yent es alu.uion w ith charcoal tubes (act is e sampli ng) nr , he missis e dosimeter 1 o es aluate the appliea bilits ol nc dosimeter osera wide range ol compounds the micsti mon included scsen dillerent organic compounds each t o serialise ol a dillerent lunctional group Included in . studs were hen/ene (aromatic), n-butanol (alcohol) . hats! ,melate (ester), isooetane (alkane), meths I chloioi m halogen.tied alkane), meths I I'ohuis I ketone ( ketone) 11, hioroeihslene (halogenated alkene) I he dittusion 1 is . ' (I)) use-d was that supplied bs the badge manu(aei . iiept m the case ol isooetane sshich ssas reported as . an unknown coelticient Computations involving i s i -npound relied on the coefficient lor n-oetane A 1 a net s ol es periments ssas conducted to look at a ss ide range ol questions. Their findings corroborated dosimeter con. ern ,m:!ar to those of aetise ssstems using charcoal tubes. < e . minimum and maximum loadings are important, postimpie cjrit.imin.itiiin and toss can occur it the exposed 'iso'hem .s not adequatels sealed, peieent recosers lm 'M in's is consistent with percent recoveries lor single om.r i i" is and ddlerences in charcoal lots can give ddter u le.uit-. Othci tests confirmed the need lor some' air t mosement .ions' the badge lace and the lack ol ellect ot icmpeiauiic changes over a sniall range (II k ) I he results ol the si mu It a neons sy tripling with t he ha dees and the c ha t coal tubes indicated that the badges had a consistent nega tive bias I he authors suggested that because the ic'iills w et c so re prod uc i hie c or rcc't ions 1 oi udsoi pt > on desoi pt i o n i 11 ie icue ies less t ha n 100 pei cell l ea n he a; i o m [ill - hed m t a ' is done tor chat; out tube data In 1979. 11 ir,i \ ,i ma ,i nd I kedn c \ a In a tc d t hi a p pin a .. m ; I the GASH \ IK 11 lor monitoi i ng exposure' ' inn d sol vents'1'" I heir research involved dilleicnl pi cp.i rations ot act i v a ted cm hoii 'p'll" m plain ot tin supplied uollcilion mt'd nun and c sposuic to no st in c s ol n-lic sa iv_ 11 In 1 ace tale and tolmne Numniatv (graphical) data indicated that the amounts ot 'oimimin.int absoihed hi the dosirnetei vvete piopojnon.il to both the vapoi eoncenti ations and time ol esposme Vlalhd.iv and Xnd'Mson repoited on tin in. ot 'I' G V B \ I H, C . a an ,n it or inp i oi ha!, a I ,u i. ' " mi- ini!i' .iiiIh .ii i; a i a 11" i il nc.i 11' im ii' - i - i mm i. i. ' plus t' ti pel i e n. U i in s. m m.pile '; . I II o ' ; i I hi I 111 11"' S d id m >1 11 p. n i i !o 11 p 1 < '1 I '11 I ol d. I in m n 1 '' i. nDi'nii, at ion ot hyloth.ine n die net atm" p'vn. . In ' j | V ,|J . .11',! lii'.'limin ICpol'C 1 1 ' on.o oi" deso' pt mu et I icic ne ies o! cha i s oal t ube s a ml t lie li \sH \ I H 11 I o' ii'iir ' ' I in m 11' id dos i net 'nev I ou mi i he d osi m. t e i to be i m il.i ' i ii i In ' ii be w tide ' o> a pot d ": i ,j ' m 'm I a mi , m p n [ip i; i t h n - a i e e c s. c d i ' i ''1 u : ' ", m t - a 1 -111 m.o 11 i > 111 m I I 1.1 b I o 11 a' ; - .1 ' :1 e 7 t.nb..n m tin i ho amt p'tiolcnm Uiiu.d a N a urn had ei I h',`V ii1 d n ot e \ pia ui w I. \ I h1 s d i II et e n. ` w > m '! .,11 e t one method ol liosme and not the other In |9St) \mlip and MnHuis ol the 'M ( timpani presi nti d i '",u Its uimp.iniii; the ' M passtv e mon it m ivlli cha r t o.i1 i he s in s.ur pi in g I oi ip i \Ui re's ol mean c com pi hi nd s '1 Ihe ta hor.itoi v tests included a biilaii nustiue ol toluene and methvl ethvl ketone. a teriiatv miviuii' ol ben/ene tolm ne and w Ii ne, and complex mixtures ot unleaded and leaded gasoline containine various alcohols Although the mv estigators cued "cxeellem " precision and accurae v lor the ditlu'ional monitor, sample sizes vvete small, and the com plicated stuilv design and lack ol raw data piceltidc the eietei min.itiv'n o! precision and bias statistics Ma/ur and his co-w oi kei s'111 conducted sidc-bv-side lahotatotv and held tests with charcoal tubes and 3M ot game vapoi monitors to measure concent tuturns ot halothane (2-bromo-2-chloro-1.1,1-tntkioi oethane) and enflurane (2-chIoro-1.1.2 inlUtorocthv) difluoromethiI ether) flit- results ol t lie laboratory studies are presented in Table II and support the authors' conclusions that the dosimeters are a reliable method for the collection ol enlltuane and ha lot bane In 19X1), I autenherger et at described DuPont's passive monitoi lor organic vapors "1' F.aeh chaieoal strip in the PRO I T K G-AA Organic Vapor Badge contains approxi mate l\ 100 trig of eoeonut-hased activated charcoal impreg nated in an ine11 po!\ mer. A dual s.impling rate ol approxi- Am Inj H*,,' AtJoi. Iflh Aut'u'-t 198? 3H 107260  11.t(oI\ h) or 100 ml nun is determined bv thl- removal ol oik1 oi both ol i hi; dosimeter's protect no cover x Oik1 aspect ol i heir research inv olved experimental determination ol the dilkiMnn eoclticicni ol several gases ,ind vapors they repotted that values calculated b> I ugg1'' were within 10 peieem ol their expenmcniallv determined vliltuslon eoellieient v.dues Ptelimin.u \ espenment.il tesulls were used to dise uss l.iee seloeits elleets. r.mee .ind sensttis us m.isintuin ,i nd minimum s.intpline times, \.tpor retention, xtor age sta hilits, desorption ellieienes, and overall hadee elheienev I he overall accuracy detei minations were limited to lout ohsv i \ anons at each ol two concentrations ol eurbon tetraehioi ide (see table II) However, the presentation ol law data as well as an esplanalion ol the stutistieal tests applied, is most useful I his same detail ol intoiniation is also lound in DuPont's validation reports lot toluene and hen/ene (see I a hie 11* " ' I n the hen/ene report. 1 )uPom also dest i ihes its pKO-1 f K C i-H H bailee 1 his badge has a backup see i ion ol e ha renal, which seises the same pmpi"c as the second section in a sh.iiso.il lube, / e . to aid in detcimimng it the sampler has been m erloaded I he J M ( ompanv also mai kels an Organic \ apoi Moituot with a backup section/1 In studies ol the measurement ol waste anesthetic eases with passive dosimeters. Jonas or at. evaluated the GASBADGE. JM Organic \jpor Monitor and On Pont Pro -1 ek in measuring eitIIurune 1,1 I mlortunaielv, the badges were not identil led in the presentation ol the results although in s i pi s uit ion ol t lie reported s.i mpler geomet rv would mdis ale i hat \ vv as t he Du Pont badge. B was the J M badge, a nd ( was the G\SB\D(iE I he results ol their laboratory siiidies indicated that badge B had the lowest eoelIicients ol \ a i i.i I ion (C V was not ca leu la ted as described in this text) as compared to concentrations determined bv infrared analy sis Badge A had a low C'V (9 percent) at 5 ppm and a much higher v a I tie I CV = 34 percent) at 20 ppm. The C badge had consistently high CV\ ranging from 2J to JO percent It should also be noted that the charcoal tube CV\ ranged Iront II to 27 percent, that desorption efficiencies for the badges ranged Irom 0X1 to I 17. and that IR analyses of lank concentrations were constantly lower than expected If badge B w as the J Vt dev ice, the results of Jonas er al. support i hose reported by Ma/ur er al' Ml Further testing ol badges A md seems necessary, however, to confirm their seemingly low precisions. Ma/ur and his coworkers conducted additional tests comparing the JM and DuPont badges against charcoal tubes Methyl chlorolorm and trichloroethvlene, two sol vents widely used in vapor degreasing operations, were sampled In the laboratory phase of the study, the badges and charcoal tubes were exposed to chamber concentrations over the range of 160 to 840 ppm of methyl chloroform and Irom 20 to 200 ppm of trichloroethylene. Exposure times varied from two to six hours for methyl chloroform and II om lour to si x hours for Irichloroethy lene. The laboratory work indicated that the percent recoveries of the various doses (concentration X time) were in good agreement except tot one exposure of the J VI badge which inv olved a fi\e hour hduyfnai Hygient! Association JOURNAL MJJ 8 87 exposure at 700 ppm I he authors n-'ted th ' this esposmi ol J500 ppm-hours exceeded ihe uppei cvp me limit put vujed by the manufacturer I he overall mc.u iccovets vulut lor each t x pc ol xa m pier wax used inomai all xnbxeq ucn held data In addition to the recovery me.isuiements, tin la bora tore phase ol this stud \ also i ir- ol \ cd d< u i mi ua i n n ol storage stability I he authors lound no xigmI ka m lox- e ol methx l e hlot olorm or tt ichloroethy lene 11 om eit In i had -J' following storage ol exposed badges lor up to thiee weeks In I97X. West and Reis/ner reported on the held test- o the MIM.MOM FOR" < R f- \l . Inc ) pe i mc.i l ion poon.i monitor lor v inv I eblonde I his inmiiioi was a mod1'', veixion ol one previously described bv Nelms ci al I G collecting medium was activated charcoal, but raiher thai rely mg on mo lee til j i dil I us ion, the badge design involved . polymeric membrane and the peimeatmn ol vim! ehloiiiji through the membrane atul ademption onto the i_h.iico.il Initial laboi.uoiy calibration was used lo deieirmne i In permeation con sta nt ol the dev ice 1 a hot a i oi v n suits null ealed good arc uiaeies as siunmari/i d in lahie II During the same penod that ! ompktus and Gold await were describing the GASH \DGI Bailee and Holnm'da Smith ol (jre.it Britain weie pie-enim;.' then uh a n i pe'tsonal passive sampler loi oigamc easts and iapo.'> Theit design involved the use ol cuhei one ol two tvpes oi membrane and xubxeq uent adsoi pi mn onto activated i ha; coal They lound two mem bra rtes to be s.i t isl.n. t m v one ol thin silicone rubber vv hie h acted as a pet meat i on iviinn nut the second a poi mis poly pi opv k nc film u hti h aib 'w,, d. molecular diltusion ol the gas and vapor I hcv coiwhut o laboratory tests using c.nbon tetrachloride sivien-. and dichlorodilluotmethane I heir test icsults do mi v some h. minology. eg. permeation rates lor both the pcrmeaiu a device and the diffusion.il device, but did provide an emit demonstration ol the leaxibihtv ol such a dev ice loi rnomto1 ing certain organics The device, the Porton Dilliu.ou Sampler, seems to see its greatest use m Great Bmam acrylonitrile One ol the new est applications ol passiv e dost met rv involves the use ol a porous poly mer ( Porapak *' \ ) as the collect1 ng surface with subsequent thermal desorption and gas chiomatographic analysis, Benson ;tnd Boyee have described such a device and its utility in sampling lor acrylonitrile ` 1 aboratorv testing for aery lomtnle inv olv ed com pa i isnn ol the dosimeter values with concentrations measured on a g.ichromulograph Initial experimentation indicated that the dosimeter can be used for aery lonit rile concent i a tiorix in the range ol 4 ppm. but at concentrations ol 2 ppm a 40 perceni error is reported. aniline In addition to activated charcoal, another widely u w I adsorbent medium is silica gel To study the utility ol tu.s material. Campbell and Kon/en conximeted passive dostm eters from glass culture tubes ( 1.05 cm inside diameter) w oh 40 60 mesh silica gel as the collecting surlaee 1l.aboiativi y testing involved exposure of the dosimetet to aniline with exposure concentrations determined by gas chroma:.) graphic analysis ol ethanol gas scrubbers Three dilleient 3M 107261 t> i 5 size ( Ix'net h I dosimeters w ere c\ aluated. w iih I he best results obtained u itb the imet mediate length tube (L. = 3 0 cm. \ 1. - 0 3 cm) "I he authors piesent raw data and clearly described then statistic.il techniques ethylene oxide Mullins and Artdcis hast' iccentlx described the 3M diftusional nuniitoi (or sampling ethx lent oxide in air <1'i' In this badge the collecting surface is described as a "chemically impregnated charcoal surface, (where) a reaction occurs pioduurtg a stahle compound with a sapor pressure sub stantially lower than the parent compound." 1 he authors present statistically summarized data describing the linearity and . a pan n \ ol the mom tot. the rec o\ ers of absorbed ct hs 1et.y oxnlx ens uonmental ellects sample stabihts and the elletts ol potential mterletences Precision and bias ate pies-, tiled in 'I able 11 formaldehyde Kodnguiz er til base described another 3M dillusmnai in on it in lor sa mphng lor rna Idclu de 1 In thixc1ilfuxmn.il riinnitoi the e o licet mg surface is an "impregnated sot bom" which can then be desorbed m \ntt with waiei and the concent i at ion ol I orma Idchx de determined colot imett ica 11 \ I a hot at oi \ e\ aluat ion I irst ms o|\ cd detei minat ion ol i rein et y coed n lents. which at eighi ppm-hours (19 3 mien am- ; wi e found to he I 00 ^ 0 04 oser six tests 1 hr ne'1 s'ep no net! detei mmation of the dosimeter's "x.imphi . oi1 ' ' I) A I l h\ exposing the dosimeter x to "known' i o i cutia11oris ol t ormalrlchx de as generated b\ a pet meal. time It.' Hint ol relatixe humidity on the samnlwn i lien yya- in 11 st mated. and exaluation ol the data did m indicate any statistically significant differences heuyeen it rales at so ,.nd 85 peicent relative humidity The sm protot ol then inx olxed simultaneous exposures ol imping (modified chromotropie acid method) and dosimeters ) t authois concluded tliat "the meastued xalucs by h.un methods lie within " 25 peicent ol the expected respond urid that "iess y.uijtion is obseixed in the monitors than in thi impingers " Howcxet. neilhei piecision nor hms wete teported "I he authors also inxcxiigaicd ellects of xtoiagc and detei mined that at e ley a ted temporal ur ex ( 3 b c (' I losses u p to i I percent occurred a I ter one w eels, how e \ er no sigml icarit loss xxax seen lor samples stored at 23 "C The authors briefly discussed the potential for a negative interference from phenol and described the use of modified calibration curves to address this problem DuPont's PRO-TFK series of colorimetric Air Monttori" o Radges. includes a badge for formaldehyde The collec t:o:i principle involves a chromotropic acid-xulfuric acid reaction l aboratorx ex aluat ion (42 samples) of the dc\ ice al xexen exposure lexclx rescaled results as shown in "(able II l'1 ` Additional studies also were conducted on tempera ture and storage effects 1 he raw data and statist ica I ana lx sis proi cduies arc presented. K riesef f" has dcxci ibed a new passuc dosimeter for lor ntaldchxdx which is a modified xeixion of the Palmes tube At t|u piesent time experimental data concerning this dex ice a il noi a . aila hie phosgene Mathetnc cr ol haxc recently described the GMD, Inc "passive dosimeter" w hich pros ides a scmiquantitatixe mea surement ol phosgene exposure.*The badge involves direct contact between the contaminated air and a chemi cally impregnated tape and therefore does not rely (in a stagnant an layer. The treated paper stain intensity is reported to be logarithmically proportional to the phosgene dose ox et a i ange of 2 to 100 ppm-mi notes For quani \t.i i o c measurements the badges can be read coloci-i tricullx other methods Hill and Fraser have described the use ol commeicial dciextoi tubes modified to act as paxxixc doximeteix In then research, common length-ol-stam detector tubes were modi fied h\ cutting off t he cornea I end ol the tube and lenmxine some of the mdicator column matei lal I his leaxex an oi il is. wuh a mis' sect io na I area equal to that ol the inside ol (fix' iuhe and a path lerigth detet mined h' :la iIki.iiiu 11 mi : m end cil the tube to the beginning ot the mdicatoi m.itx i ml ()rii' would expeit. howcxet. that .is tl.e sinK-n1 ni.ite.ia! becomes exposed ir. the length ol 'tain metea'c's tin diffusion pat h length w ill a I so increase, t hei ebx t fia ne mg t lu sa'..pilin' iaie I lieir exaluation of these dex ices mynlved sepaiate labmatotx exposures to toluene ethanol and txo pi opa nol T In i C' lilts of then w oi k , ah hough pi esent cd only in tM.iphn;il sm nma i \. demon si t ate llie pot! Ill ;al for the Use ol mod 11 u`d com me' t la 1 detei t oi I nhyx a x pjxxi \ e <1 o> i nu i. is field validation R ela l ix clx lew si iid ics hax e been published m xx huh passi y e dosimeters haxc been compaicd side by side with chaiconl tube- oi other com ent ion a i sampling methods under aemaf field xondiiioris for inoigame compounds only txvo xtudii s myoixing nittogen dioxide' and chlorine, h.ixc been identified Foi oiganic compounds, cighi siud iex' 4 'J11'"f'" hax e inx ol\ ed f icld c omparisexns y\ uh t he number of compounds per study ranging horn one to 22 In three of these studies, statixtual analyses ol data were noi pi esent ed and cannot be performed beea use of sma II s.i m pie size oi iMxiillicient presentation of data Tones n conducted a field exaluation for NO.' in a sail mine, which contained diesel equipment as the NO. xoutee At each of 16 different fixed area locations, txvo Palmes dosimeters and txxo TFA tubes xxith pumps were used to sample the atmosphere The act ix e sampling (pump) method gaxe a coefficient of xanation (C'V) of 8 7 peicent while for passive tubes the CV was 5 8 peicent Regression anah six (w here the active sxstem wax the X variable) of iheir data gixex a correlation coefficient of 0.69. a slope of 0.59, and an intercept of 2 05 ppm for data ox er the range of 3 7 to 5 5 ppm as sampled b\ the actixe method, T hix indicates that the dosimeter gaxe consistently higher readings which is reflected in the means for the two methods 4 51 ppm lot paxxixc and 4 14 ppm lot actixe sampling The authors did not report wind velocities, bin low velocities, as would be expected xxith area samples, should haxc caused passive etc 4ir fnc hyf 4.w; Jill Kjzu'' 3M 107262 values lo be low as compared to active values, this was not the case On the other hand, high face velocities could have led to the observed positive (passive versus active) bias. Haidy ei ala>i> reported the raw data results fiom a field ev alu.it ion of a pet meat ion chlorine monitor (R t A l.. Inc ). Thu teen com pa risons were mademwhichtheresultsfroma battery operated pump and an impinger sampler were com pared with the measurements from either two or three per meation samplers. To further evaluate their results, the investigators performed a regression analysis using their permeation sample means for each comparison as the dependent vanuble T he rcsuhsarc quite good with a corre lation coefficient ol 0 95. a regression slope of 0 K5. and an mteuept ol 0 15 ovei a range of 0 05 to I I ppm as delected by the impmgci, It should be noted that with five impinger samples oi less than 0 I pprl). the eoilesponding permeation dev sees detected consulei abh higher concent iat ions (0 16 to 0 4 ppm) Silveivteinl Hl teported Held results lor aery lomtrile moni toring using 18 paired samples ol GASBADGF passive ntonitois and active svsienis (charcoal tubes and pumps) over a r a ngc ol 0 8 to 5 8 ppm as deter mined by the active method ] he differences in results using the aclive system as a r el ei cnee ra nged from "0 7 to I 5 ppm 1 he dtf fci cm e in mea ns, 2 18 foil he passiv e v ei sus 2 75 lor t he act i v c s \ .] i m, was 25 peieent f urthei data wete not presented West and Reis/nci reported five seis of field resell lor v my I chloi ide sampled w nil permeation dosimeters ( R I VI Inc ) and charcoal tubes1'1 Further interpretation ol i* . u results is presented in Table III In each case data to rhe aclive system are the X values hour of the corn!.. . mi coefficient v a lues arc \ cry near one, reflecting good no ; la lion how ev er. t he slopes show quite a large degree oI \.- ,a bilny (0 69 to I 51). indicating that badge values m.i \ tall either well below or above charcoal tube values In those cases w here the slopes were less than 1.0. vcry high hun,idities (67 to 91 percent) were reported by the authors I his (actor mav have interfered with permeation, although the authors icported that humidity had no effect in laboiatoty validations: hence the variation in slope remains unex plained The authors noted that the overall field results showed that the badges had a slight positive bias Hickey and Bishop exposed 78 pairs of side-by -side char coal tubes and 5N1 Organic Vapor Monitors to complex mixtures of organic chemicals in tire manufacturing opera tions 191 Generally the sampling period ranged from three to TABLE III Regression Analysis of Vinyl Chloride Field Data12' N Range (ppm) r Slope Y-Intercept 7 0 02 1 0 99 1 19 8 0 08 1 8 0 99 0 69 12 0 02 6 9 1.0 1 31 39 005 1.8 0 82 0 81 24 1 48 16 7 0 96 1 08 0 03 0 05 0 01 011 0 43 Amencjn Industrial Hypifnp Association JOURNAl (43'8'82 five hours, and nu>s* oh sc \ \ ai ioiiv consisted of one mon 11 < and the time weighted average eoncenuution liom iw sequentially exposed charcoal tubes Sixty-lour ol the sc were personal samples, while the lemainmg 14 ueie au samples The samples were collected in two separate plan (50 sample pairs in one plant and 48 m the other) Of the organics potentially available for analysis. 10 were dctecu over a sufficiently w ide range of concentrations to allow tr apptopriate statistical analysis by linear regression U results are interesting in thai in the first plant. 9 of ihc I organics measured by the dosinteteis showed highei vap, concentrations as compared to the ehuieoal tubes whiU > the second plant only tluce substa rues had a iegression -.!<>; greater than one. The combined dala for both plants did u. indicate that the passive system was consistent|v hi.isi when compared to the aetive system T he authois did pun out that generally the T-inteicepts (5 passive dosimen data) were slightly negative a finding u Inch mav indicau lack of sensitivity on the part of the dosimeters at lo concentrations, for the remaining 12 compounds pain t-tests revealed no significant dtffetenee between the ch.i coal tube and passive momtoi means at the 96 peioi confidence level The use of t-tests to analyze such data h been quest mned since t he means ol the t w u met hods ma v I very similar hut the components of paired values can h considerably different 1191 This condit ion ca n onlv be rev call through regression analyses In 1980. Ma7Ur el a!.'4'' repoited limited field data b halothanc and enflurane measuiernents using both -v Organic Vapor Monitors <(>\M) and an active svsur (charcoal tubes and pumps) for halotham three pan. samples were reported. The mean conccnuation for tb active system was 2.01 ppm while I 9 ppm was repotted !< the OVM. a difference (relative to the active svstem) ot fiv percent Only one data pair was reported for enflura ne 0 4 ppm for Ihc OVM and 0 52 ppm for the active svsten Obviously, more data are needed to draw conclusion regarding a comparison of the two methods for these ag'cni A second study by Mazur el a!1,1,11 reported field ronip.n isons of passive dosimeters and active systems (pumps an charcoal tubes) in sampling for trichloroethy lene (T CF ) an methylchloroform (MC). Both DuPont PRO-TF.K and 5N Organic Vapor Monitors were used for the passive sv stemPersonal samples'included exposure of one each of all thie monitors. Area sample results involved three average valueone was the average of three charcoal tubes, and the othe two. the average of two of each type of dosimeter, Fot MC 11 personal and 7 area data points collected over time pen ods of I to 5 hours at 15 to 21 C and 55 to 40 percent relativ humidity were reported For TCE. 22 personal and 7 are data points collected over periods ol about I to 6 hours at I to 24 C and 50 percent relative humidity were reported / regression analysis in which the charcoal tubes were th independent variable was reported by the authors. In each o the following data sets the presented values involve TCT personal and stationary sampling followed by MC persona and stationary sampling For the DuPont badge, reeressto 3M 107263 slope' of I 0, 0 99, 0 99, and 0.98. and correlation cocfficicntsol098 0 98.0 94. and 0 94 w ere obtained FortheTM midge ugiession slopes ol I 08, 1.06. 1.07. and 0 90, and oru latmr, coefficients of 0 98. 0.98, 0 98. and 0 90 were del i'i m incd I hesc \ a lues appear to be quite pood, bower er. tin ,tntIkn s <)id not report if the\ tested the statistical sigmf i- ntn. c ol these sallies They also did not report average ol t.K. si lo, r ies associated w it It stationat s samples I .mi' ill ,fJ`' ol Great Britain reported field validation l.o- ti . 1`orton diffusion dev ice ss hilc measuring methyl -it In this case the conventional sampler was a , .1 lassette fitted with a charcoal cloth similar to 11 the F'onon device A regression analysis pcitr ihtit data showed good cotielation (0 9) and . ') 9) howevci. the intercept value (4 69) mdii a low concentrations, the "home-made" dev ice e - s .dues than those determined with the convcn- oi ('oncentiations repotted for the comm langed liom I I to 189 ppm out Bovee''''field tested the Monsanto I'uiop.ih . o . 'neat B'ltam C'onv entional samplei s i onsisn-il ; 1; I I'ot opah N poly rnei tubes Sivlv -fiv e pa ii s ol .1 i ohiamed. and ihe range of acrvlornt i lie mea e :t ` .nhcswasO |3to2l 6? ppm Regression ana lv- o 1 t'. 1 data indicates onlv fan coiielalion (0 63). a low o , ( , "d a negative mteiccpl ( 2,06) "1 hi"- values f. ` i ul, Horn the appaiem inahihtv of tlu pu.w . ' ' , a, 11 , v detect ( oneent rat ions less t ha n 0 o ppm V- . : ;, p.i i, si ms between values over the lowei hall <>! ok e: : a i .oik sa m pled show ed Considerable scattei I lu final field si udv to be d iscussed suggests pci haps the oust si. i ions disc icpa ncics resulting from use of chauoal vassi v e dosimetei s ' f Ins studv was performed bv NIOMI sersonnel in coniunction with industry-wide studies of the 11 v -i lea nine sc i een pi ml mg, and boat manufacturing md usties and also included one viscose tavon and one cello 'll,me plain < urbon disulfide, perchloi oethv lene toluene net by 11 sc hut \ I ketone ( M 1 BK 1. stv rene. and acet oik w et e ampled usmg the 1M C)\'M, the GASBADGl . and active v stems w n h charcoal tubes 1 he presentation of Ihe studv Ifs ign is not clear, blit it a ppea i s that area sa mples involved all three devices while personal samples involved chateoal uhes and or.lv one of either passiv c dev icc. In that this studv nvolves six compounds in 64 plants, the volume of data is ,uite large In addition to icgression analvsis. paired t-tests nd Vi ileox signed tank tests were performed bv the authors o determine equivalence of data sets As noted earlier n fse ol '.-tests lor determination of equivalence has nt i questioned liq Table IV showsthe pnmarv resultsol this studv Ascan be seen, the range of correlation cocllicicnts (r) for mosr com pounds was quite large Although 12 plants were sur- eved loi toluene and MIBK. the data ere grouped lgethe; and therefore range- of the coi lelation coefficients ould not he dcteimined For carbon disulfide, one plan! as su i v ev ed vv it h t he OY M a nd G AS B A [Xi F., a nd one w as invest'd with the GASBADGF onlv For the ranges of i potted m I able IV. ihe uppci values are quite acceptable. w ii h t he exception ol eai bun disulfide using the G ASBAI )G T Howevci. the conelation coefficient for carbon disulfide using the OVM was 0,95, The conelation data can be summed up as being cxtremelv variable Table IV also reveals that concentration had an effect on the correlation coelficient for threc of the compounds, though this was tr ue for both monitors onlv w hen measut ing acetone concentra tions Kcgiessmn slopes were as variable as the correlation coefficients T he authors tested the slopes to see if tfiev were significant!) different from zero and for aeciuric and tarbou disulfide a d lit ci enee could not be demonstrated for sc v eta I of their data sets T his indicated tti.it tlu-re was no iclationshi p tic t w een I tie results obtained vv it h the act tv e sv stem a rid those obtained with thi passive dosimeter 1 ot other com pounds it w on Id have been use I ul t o test t he d il let erne ol the slope I tom one, which if not signif icwnlls difleterit would indicate agreement of the two methods I ri tests of equiv a lenee of data sets the author' noted t ha i (oi all plan! data combined onlv toluene slnmcd iiiiial.lv a nd l h is f oi t he i ha i eoa I Hi he - G A S B \ PG I l ( I (.It) mmp.iiison llowe,ei. when icmiIi-. liom individual plant' ate used, the i > >mpu t isori iniuoiuo ate quit' vanahie I oi peri blot oethv lene equaluv was repotted lot one of ihree ('[ B(. i om fiat'son s and foi oin of Two t 1 ;M sets f si stviene. two o! six Cf-GB and no CT-FM i oinpa i isons sfiov --d i-Li ua Ills lor acetone I h i or ol 11 v e ( ' I tMinmpan sons and one ol s>\ ( I -till data set- showed equaluv It. addition (i B f \ M .`onipa r tsoris show cd eqtia lit v ui6o` !" i om pan son- 11 is oh \ io ii- t ft. 11 11 p. a1 a hm l v was no' demonsuued in the studv Wheihvt the pioblcm mvo' es tin do-imetets. mv est iga t iv e ot laboiatoiv techniques and oi env ii on mem a I eond it ions ca nnol he dilcr mined I n l he onlv other field studv of mote than one plant Mirkev and Bishop' also icponcd some problems w it h the consistent v ot obsei v at ions These limited results f lent I v demons! tali t he need foradditional field stud ies of passiv c dosimeter s ns computed with standard monitoring techniques discussion F'assiv e doximet rv (monitor mg I is a ta pid Iv dev eloping technologv as witnessed bv the pi ohferat ion of devices and applications since F-'almes and Gunnison introduced their concepts |ust under ten years ago The latest entrv into the field comes from the MSA Com pans and involves an adap tation of their length-of-stain direct reading tubes for inor ganic gases16'21 which incorporates the application of moleculat diffusion and a chemically impregnated paper as the sampling medium Although rescatch texults are not availatrlc. as a fust approximation one might assume that these dev ices have precisions and biases similar to those of con ventional detector tubes For anv new technologv to be accepted and used hv piaitiiing professionals, the development of a body of knowl edge demonstrating cfficacv is necessary With env itonmental monitoring techniques, the determination ol the efficacy usually starts in the laboratory and culminates in the field In the case of passive monitors, a hodv of know ledge based on laboratory testing is rapidlv being developed Of lire vari- t-rr in? H\r A'\o.' }9' 3M 107264 TABLE IV Major Results of a Field Study for Organic Vapors'*01' Concentration Substance Comparison Overall r Range of r Dependency Potchlofo .ylen O i > r ene A * irme 1 ' r | |H V* <' CT GB CT 3M CT GB C7-3M CT-GB CT 3M CT GB CT-3M CT GB CT 3Ml CT GB CT-3M 0 62 0 86 0 82 0 76 0 38 0 45 0 80 0 91 0 88 0 79 0 30 0 95 0 62-0 99 0.84 0 94 0 65-0 97 0 48 0 86 0 36 0 86 0 25-0 83 NA NA NA NA 0 03 0 38 NA Ye^ Yes Yes Yes a!' that have been studied, three appeal touniquclv allccta >' `' a-- ion mi mi 1101 'i accuracv iti measuring an hot ne concenI'.rmiM of gases im vapois. The most impoitant (aclot to he determination ol the contaminants' diffusion < i" Hu nm <i'i the sampling; rale when the dosimeter's gr mnviry is also eonsideied). the wind \docile at the d'smieiei lace a nd the relai ive humidity oflhe sampled air V discussed earlier. there aie also a variciv of poter.iial sources ol ei i 01, sue li as mtei tcring eemia niina nis, soi hem e a pa. it \ and pi oblems assoc lated W ith analMical deter nnnations, which an common to both passive and active mcaMiieinenl techniques I a hoi at 01 v deiei mi nail on ol sampling rales ( D A l ) lor a speeilie ntonnoi and a spetdie contaminant are important and a i e heme provided b> sev era I dosimeter ma nufact mers lot an ever increasing number ol compounds Once an u ppr opr ia(e sa mplirtg rale lias been delei mined, corieci ions Im in Id use specifically lor lempetature variations, can be made 1 he main pt oblcm vv ould mv olv c sit un lions w her c I he env itonmenial tempeiaune lluciuaU'd widely (more than 2? ' C) and uenl unnoticed, a very unhkelv condition The research on effects ot face v clooties demonstrate ihat few pi oblems should be encountered where dosimeters are worn by workers as personal monitoring dev ices "2'',`l I lieu use as area monitors should be caiefully evaluated to ensure that stagnant atmospheres (velocities less than 7 5 cm seejate no! involved Migh w ind v clocitics (at least w hat would normally be encountered in the workplace) or wind direction do not appear to have adverse effects on dosime ters with wind screens Ol greatest concern as a result of reviewing the literature on laboratory testing of passive dosimeters is not the results but rather the thoroughness of their presentation. As dem onstrated in Tables I and II. where statistical analvscs arc pi esc nt ed bv researchers, or where sufficient data are pre sented to allow the reader to determine bias and precision, the tesults are very encouraging linlonunatcly the presentation ol experimental design, as well as sufficient data and or statistical analyses, aie often lacking. This is tine lor some indn idual researcher s a s w n] ,i-1 ui sc \ ma I ma nulac t u 11 i . the dev ices, especially those toi innipuin compounds 11 m recommendation regarding laboiatmv lestmg is nunk wmild he ihal those rescaiehcr s muilvod m the tvahiatnm i passiv c dosimeters m the la hoi atm y take the time to t ep" the conditions of their expcimunts. espeeiallv equipntei used and procedures for determining ' k now n" conei m i. lions, and as much detail about their results as possihh summarized data ate presented ihcauthoi should piesei the known concentration al c.u h level where levels a: determined hv concent t al ion a nd i mu i In mi tnbei of i Tim v at ions ntade w il h passi v e dosmu tei a no i; e a v e i ,ii > v ,i and standard deviation ol tin k .utk. Si.iI'sih.iI an, i again HI each level tested shoukl involve deiei mma I ton > the coeflieieni ot vaiiation (precision) and the hue . described in equations (7) and (K), icspeciivclv Oikc il ev alualions are made a i ihc vanmis uvi lev els tin del ei m nation ol a pooled precision and bias is appropimie I addition to these measurements icseaiehets mav alchoose to pi event an o\ ei a II wskin im u t acv 1 o dev. log heller Understanding ol appiopnate siali-.tieal trihi, ,u and iheir application to passive dosimeiiv a icvi- l.autcnbeiget e/ al is kvoiiihh inf d bor mosi active moiutoiing no. n .ed m on!, hvgiene the random sampling emu e mu.ok asm ,a: with the pump and IS I radii imta llv SCI a! s 5 per. in1 I many cases especially Im tin measiiH mem ol oo .o ' vapors, i he ana Iv tiea I piocedmcs and . miseqtt. nl r, a ssoeia | ed eri ot s a i e eq u i v a k u1 n I i I, pa o. i, i ,. n,, i systems Nevertheless, (null sv .hums hav. i.iihIou, ;o consequent Iv, one should nm expect j. e M t i i agovi the results ol eompaiisons obtaimd iindu In id h m , turns Anolhei taetoi com plnal i hi tin i valuation o H results is the gieaily ini teased pussihiktv Im iheuinodu I ion ol opera I or ot sy sterna l ic e 11111 s S i m e act i \ i s \ n 11 require met liamcal pumps I he jiou m u I f in np( nil,' , would seem I o hi' gi ea t e i i ha n I m ji.o o v e uvimi'- Oveiall. il is apparent thal existing In Id nloi companng passive dosimeter, with viand.ml immior meihods ai e highly v a i ied Whih sonu si ud u '. dv1 un1 n i r ,> good cortelaiion and slope'"'''' oiheis show onlv r. correlation.'' or aie extiemclv vanedlm both eaicgoi u C'ollectiv ely. I hese references neithet suppmt nor teUin tl use of passive dosimeters Certainly environmental lack' a fleet act i v e sy stems as well as passiv e sv stems In tin o i > case can be made that cnvirmmieni.il laetms (wind an humidity ) affect passiv e sy stems io i lie gteaiesi e\tent w In temperature and pressure vuiiutiom most gieatlv alh active systems. On the other hand one can also sink ih poor experimental quabtv control mav alien such lai tor , contamination, time measurement cum and an.d ii, error. Of course, chemical miei lei cnees mav ,d k both sysiems As With laboratory e xpi i mienta l in. 11 v oiiiii ie inir n ( regarding the field icsiing ol passive dosmiciers involve plea lor better reporting ot hoi h I icld eond it ions a nd a - ul of ana ly sis, birsi. lor both pci son.il and a rea moniionnr 11 estimation and m mcasuicmem of lace veloiitv is impo Anipft'^r influklitdi As^ooai.iv' JOURNAL Ms" f V 3H 107265 tant Of equal importance is the reporting of airborne con.arnmanis other than the one(s) of interest and en\ ironmen:al \anables including temperature, pressure, and relative humidin along with information as to their variation over ,hc period of observation Again, if raw data cannot be iresented, the repoited results for each level tested (X value us determined b\ the standard method) should include the lumber o( ob.scrs atioris made with passive dosimeters, and heir associated mean and coefficient of variation. Statistical `valuations also should include a regression analysis of the data as outlined earlier Undoubtedly, additional research is needed on the effect of not considering the error associated s ith the supposedly independent (X) variable. I n summars, passis e dosimeters show great promise as an mportant tool The results presented in Tables I and II .ndicatc that the precisions of the dosimeters are essentially equi \ a lent to cons ent mnaI techniques and in many cases the additional five percent errot associated with mechanical umps makes passive dosimeter systems even more attracisc This, coupled with their ease of use. lack of required inintcnanee. acceptance b\ workers due to light weight, and nneeessarv calibration make passive dosimeters extremely 'dsantageous Certainly the\ will not replace conventional nethods, as these have then place, especially for area samling The i. ontinucd a nd grow ing use of passis e dosi meters, owe v et. should generate additional data documenting their chahilitv and eliminating doubts about their usefulness cknowledgement he assistance of I)i H Kenneth Dillon. Head. Industrial fsgtenc C'hemistrv Section of Southern Research Institute, n critically rev iew ing this paper is gratefully acknow ledged eferences 1 Tompkins. F.C. and R L Goldsmith: A New Personal Dosimeter for Monitoring ot Industrial Pollutants Am Ind Hyq Assoc J 38 371 -377 (1 977) 2 West. P W and K.D. Reiszner: Field Tests of a PermeationType Personal Monitor for Vinyl Chloride Am Ind Hyg Assoc J 39 645-650(1978) 3 Lugg G A.: Diffusion Coefficients of Some Organic and Other Vapors in Air Anal Chem 40 1072-1077(1968) 4 Montalvo, J G . Total Elemental Content Passive Personal Monitors Am Ind Hyg Assoc J 40 1046-1054 (1979) 5 3M Company: Organic Vapor Monitor Sampling Rate Vali dation Protocol St Paul, MN 5 Jonas. L.C., C.E. Billings, and C. 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