Instrument of Air Monitoring

CHAPTER 12
INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR
This chapter describes direct-reading instruments that can identify and measure the concentration of specific compounds in an airborne mixture. Basically this includes two types of instruments: Gas chromatograph (GC or GC!mass spectrometer (GC!"# de$ices that separate the airborne compounds so that each can be identified and its concentration measured as the separated compounds pass through the detector. %nfrared (%& instruments where the wa$elength of the emitted %& radiation can be ad'usted to match the wa$elength that specific chemical compounds absorb the %& radiation. #ince many chemicals ha$e a characteristic absorption wa$elength( this method can pro$ide an accurate method of identification. )dditionally( since the amount of %& radiation absorbed is proportional to the concentration of the chemical( these instruments pro$ide concentration data.
)s noted in pre$ious chapters( there is some o$erlap between these instruments and the de$ices co$ered in earlier chapters. #pecifically( many %& de$ices are a$ailable that are set to emit 'ust one wa$elength of %& radiation and thus are specific to one airborne compound. )s an illustration( direct-reading instruments for carbon dioxide (C*+ often are based on the %& principle( and they use the absorption of %& radiation at a wa$elength of ,.-+ 'am to measure the concentration of C*+ in the air. .owe$er( these instruments are co$ered in detail in this chapter (instead of Chapter /*( 0%nstruments with #ensors for #pecific Chemicals0 as part of the o$erall discussion of %& instruments. The GC( GC!"#( and %& instruments that can determine the concentrations of multiple specific compounds in an airborne mixture are high-end de$ices that are expensi$e and sophisticated and can be complicated to operate. Generally( they are only used when less expensi$e and easier to use de$ices are not ade1uate for the monitoring 'ob. Create PDF files with ! t this "essa #e $% &!r'ha si(# ( )aP
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.12 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR 8hile these instruments ha$e important differences( they ha$e se$eral characteristics in common: )ll are designed to be used with a personal or laptop computer either to operate the instrument or to manage the data. The compound identification and measurement steps in$ol$e comparing the airborne sample to stored calibration or library data( and so a computer is essential for this step. They also generate large amounts of data for each measurement( and these must be processed in a computer. 8hile many configurations and options are a$ailable( the sampling practitioner generally describes their needs (compounds to be sampled( possible interferences( operating conditions( etc. to the manufacturer( who first determines if their technology is a suitable fit for the application. %f so( the manufacturer:s technical staff then selects and configures the instrument to meet the user:s specific needs. ;or this reason( there is less need for the sampling practitioner to understand the $arious instrument options with the goal of selecting these options on their own( as is typical for less sophisticated direct-reading instruments. <$en though these instruments are the most sophisticated direct-reading instruments a$ailable( they still are not designed to identify the components of a completely un=nown or 0mystery0 airborne mixture. The instruments achie$e their accuracy in identifying and measuring the concentration of indi$idual chemical compounds by being calibrated with the specific compounds they are measuring. ;or all of these de$ices( daily or more fre1uent calibration using a =nown calibration gas mixture containing each of the components of interest is recommended for optimal performance. Because of their si>e and complexity( they are not routinely used for direct occupational exposure measurements of breathing >one concentration. "ore typically they are used for area or source sampling? for en$ironmental reasons? at ha>ardous waste sites? for field determination of the composition of an airborne mixture for real-time respirator selection decisions? or as an aid to understanding the total @AC reading of a less sophisticated instru ment such as a photoioni>ation detec tor (B%3 . There are some 4%A#. occupational sampling methods for field GCs? one is described later in this chapter. ;or integrated samples( a personal pump can be used to fill a sampling bag for analysis using the GC or %& instrument. The instruments described chapter meet these criteria: in this
They are 0portable0 in that they are battery-powered and can be carried around in the field or set up in a temporary location. They can measure airborne contaminants( although most can measure 0headspace0 le$els ($apor collected abo$e li1uid or solid samples ( and some can analy>e li1uid samples directly. They are commercially a$ailable( fieldready technology. PORTABLE GAS CHROMATOGRAPHS (GCs) )s discussed in Chapter /( gas chromatography (GC is a common laboratory analytical method for gases and organic $apors that are collected using charcoal tubes or another sample collection de$ice. The GC operates on the principle that a $olatili>ed sample is mixed with a carrier gas and
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PORTA3LE GAS C4ROMATOGRAP4S *GCs.15
Figure 12.1. 3iagram of a typical gas chromatograph. (Courtesy of %nternational #ensor Technology.
in'ected into a column that separates the components in the sample according to the time it ta=es the component to tra$el through the column (;igure /+./ . )s the molecules emerge from the column( a detector measures the amount of each material. An a chromatogram( each emerging compound is represented by a 0pea=0 based on its elution time. Component identification is made using a data 0library0 de$eloped by in'ecting samples of =nown chemicals into the column and measuring the tra$el time for each. The concentration of each material is represented by the area under its pea= on the chromatogram (;igure /+.+ . ;or laboratory GC units( a wide choice of columns( detectors( and operating parameters such as temperature programming gi$e the GC the ability to identify many different chemicals( especially those in mixtures. Bortable GCs as described in this chapter focus on modern( high-end portable gas chromatographs. #ome earlier field GCs were relati$ely simple instruments that essentially added a short separation column maintained at ambient temperature to a B%3 instrument. These simple units ha$e been supplanted because they do not pro$ide much ad$antage beyond the direct-reading instruments with sensors for specific chemicals discussed in
Chapter /*. The GCs co$ered in this chapter more closely resemble laboratory instruments( with heated columns( temperature programming( and a choice of columns and detectors based on the compounds of interest and possible interferences. These instruments re1uire a computer to control the de$ice:s operation and pro$ide the data management system. #ome re1uire a laptop computer to be used along with the instrument in the field( while for others an office computer is sufficient to transfer information between the de$ice and computer. The instrument manufacturer supplies a proprietary software pac=age that operates the GC( collects( stores( and processes data( and then downloads it to the hard dis= dri$e. These GCs measure concentrations ranging from parts-per-trillion (ppt to percent (C le$els. #ome allow continuous( unattended operation or can be controlled from a remote location using a modem and communications lines. These sophisticated( computer-controlled instruments pro$ide the functions that are described below. Instrument Calibration. The instrument should be calibrated with each chemical that will be measured in the field. 3uring this mode( the system introduces a sample of a =nown calibration mixture into the
.16
PORTA3LE GAS C4ROMATOGRAP4S *GCs.1. system and performs chromatographic analysis either when the user initiates the calibration cycle or at preset fre1uencies. The instrument then displays this calibration chromatogram( including the name( concentration le$el( and retention time of each compound in the calibration mixture. The area under each pea= is integrated( and the concentration le$el of the standard is assigned to this pea= area. There are two calibration methods commonly used/: "ultipoint calibration is most accurate. %t in$ol$es introducing se$eral different concentration le$els of a chemical to the GC and plotting a cur$e of pea= areas (hori>ontal axis $ersus concentration le$el ($ertical axis . 8hen an un=nown concentration of the same chemical is detected in the system( the area obtained is compared to the calibration cur$e to determine its concentration le$el. This method is $ery accurate and can co$er a large concentration range. #ingle-point calibration method is often used for portable gas chro-matography. %ts accuracy within a reasonable concentration le$el range is satisfactory( and it is easy to perform. ) calibration cur$e( similar to the multipoint cur$e( is drawn using only two points. Ane is >ero with an assumed area pea= count of >ero. The other point is the point area obtained when a =nown concentration of the standard is in'ected at its concentration le$el. This cur$e is used to calculate analysis results. This method is relati$ely simple and re1uires only one concentration for calibration. #ingle calibration is a$ailable for all instruments? multipoint calibration is an option for others. #ome de$ices ha$e an internal cylinder containing the calibration mixture( while others use an external cylinder or calibration bag sample. Calibration gas mixtures can be purchased from commercial suppliers or prepared by the sampling practitioner as described in )ppendix B. ) 0ready-to-use0 calibration mixture is most con$enient to use( or a higher concentration mixture that is diluted by the sampling practitioner with pure air into a calibration bag will gi$e more calibration runs from the calibration cylinder. The concentration of each gas in the final calibration mixture should be near the concentration of interest. Chec= with the calibration gas supplier to determine if the compounds will be stable in the cylinder when blended at the desired concentrations. Sample Collection and Injection. The instruments may offer up to three different ways for sample introduction: 3irect on-column in'ection using a syringe. There are different syringe types for air samples and for li1uid samples. @olumes of air samples in'ected to the column are typically +mD or less( while $olumes of li1uid samples in'ected to the column can range up to +uD. )1ueous and soil samples can be extracted with an organic sol$ent prior to direct in'ection. Esing a concentrator, which is a small tube pac=ed with an adsorbent material such as Tenax( attached to the internal sampling pump. The airborne $apors are collected on the concentrator( and then they are desorbed into the column by re$ersing the carrier gas flow while heating the concentrator. This process is also called thermal desorption. This techni1ue allows 1uantification of lower airborne concentrations than can be measured using a syringe or direct (loop in'ection. #ampling time using the concentrator $aries from /* seconds to /* minutes and can measure concentra-
.17 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR TABLE 12.1. Typical Sampling Times for Portable GC nstruments! Typical #ampling Time( seconds Concentrator0 Dow "edium .igh #ampling 3irect "edium (*.5-5 ppb (5-5* ppb (5*ppb-5ppm Doop %n'ection )ir 6** /+* /* /* 4) 8ater +** /+* 4) /* 4) #oil +** /+* 4) /* 4) 0 The longer the sampling time( the more sensiti$e the analysis will become due to the higher le$el of contaminants collected on the concentrator.
tions ranging as low as parts per trillion (ppt . #ample loop in'ection( where the internal pump draws an air sample into a fix $olume loop( which is subse1uently in'ected onto the column. The $olume of the loop in a typical de$ice can $ary from *.*5 cc to 5.* cc. Table /+./ shows typical sampling times for different in'ection methods. )n instrument with a heated in'ection port can handle less $olatile material than can an instrument with an in'ection port that is maintained at ambient temperature? a heated in'ection port is re1uired to analy>e li1uid samples. Chromatographic Separation. %n this part of the process a carrier gas (also called the mobile phase) is used to mo$e the components through the column to the detector. The highsensiti$ity detectors typical of portable GCs re1uire high-purity carrier gas such as helium or hydrogen. Generally( a small internal cylinder holds enough carrier gas for ,-F hours of operation? the internal cylinder can be refilled in the field from a larger compressed gas cylinder. There are two types of columns: pac=ed? and capillary. The pac=ed column( typically /!F inch in diameter and up to +* feet long( contains an inert solid support that is coated with a li1uid material. The capillary
column is a $ery narrow tube (Glmm in diameter that may be o$er /** meters long and contains a coating on the interior wall of the column. The function of the column geometry and coating is to control the mo$ement of sample molecules so the optimum separation is achie$ed for the materials of interest as they emerge from the column (;igure /+.6 . The stronger the interaction between the compound in the $apor phase and the stationary phase( the more strongly the mo$ement of the compound will be slowed by the column( and therefore the longer its retention time. ;igure /+., shows different column types( and Table /+.+ lists some commonly used stationary phases for GC columns. The pac=ed column can accept a larger in'ection $olume( but the capillary column has better separating power. )s an example( ;igure /+.5 shows the difference between an analysis of gasoline $apor using a pac=ed and capillary column. %n some instruments( two or more columns are installed at the same time. %f a nondestructi$e sensor is used( the columns may be connected in series? otherwise they can be mounted parallel and a sample splitter used. Ese of more than one column for a single analytical sample run permits better separation of some pea=s. %t should also be noted that columns for portable GCs may re1uire special shapes and si>es( materials of construction( and other features to fit a
PORTA3LE GAS C4ROMATOGRAP4S *GCs- .1/
Figure 12.". Chromatogram!pictorial separation of ben>ene and toluene. (Courtesy of the ;oxboro Company.
Figure 12.#. Bac=ed and capillary GC columns. (;rom The ndustrial En!ironmentH ts E!aluation " Control, 4%A#.( Cincinnati( /I-6( p. +J+.
.11 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR T)BD< /+.+. Commonly Esed #tationary Bhases for GC Bhases )pplications #i$uid #<-6*( A@-/ (methyl silicones .ydrocarbons( chlorinated hydrocarbons A@-/( #<-5, (methyl!phenyl silicones B).s( chlorinated pesticides( hydrocarbons Carbonax +* " (polyethylene glycol Bolar compounds such as esters( alcohols ;;)B( #B-/*** (polyethylene glycol terephthalate Bhenols( $olatile acids Solid %&ac'ed Columns (nly) Chromosorb( Borapa= series (styrene! @olatile alcohols( =etones( hydrocarbons( di$inylben>ene polymers halocarbons (boiling points 6*-/**KC Carbon molecular sie$es (Carbosphere( L-C5 hydrocarbons #pherocarb( Carbosie$e Borous silica (Enibeads( Borasil ) L-C5 hydrocarbons dimensions (length and inside diameter . Custom si>es and pac=ings can be made for special sampling situations. %n most high-end portable GCs( either a constant-temperature heated column or temperature programming is used to enhance separation. Temperatures abo$e ambient temperature increase the $olatility of the contaminant molecules? and temperature programming( which in$ol$es increasing the temperature of the column in a predetermined manner as the analysis proceeds( enhances separation of many complex mixtures because the lower-molecular-weight compounds mo$e through the column at the lower temperature( while hea$ier molecules begin to mo$e more 1uic=ly as the column temperature is increased. The ideal situation is to choose the operating parameters to yield sharp and narrow pea=s that are easy to identify and 1uanti-tate for the materials of interest. The separation is primarily dependent on the type of column and its pac=ing or coating( the column length( the flowrate of the carrier gas( and the temperature characteristics of the system. These $ariables can be changed to achie$e optimal separation of the components in an airborne mixture( but it is critical to calibrate the de$ice with a =nown gas mixture under each set of operating conditions and then store the calibration
;igure /+.5. Gasoline $apor analysis on pac=ed and capillary columns. (Courtesy of .4E #ystems( %nc. specific application. %n most cases( columns are pro$ided by the instrument manufacturer and are described in terms of column type( the pac=ing or coating( and their
PORTA3LE GAS C4ROMATOGRAP4S *GCs.18 data in a data library so the proper calibration data are used for each sample run. Ane feature a$ailable on some field GC units is the ability to bac=flush the column to shorten the analysis run time and also pre$ent hea$ier compounds from reaching the analytical column. Bac=fDushing re1uires two columns: a shorter pre-column and a longer analytical column. They are usually connected in series with a 0tee0 fitting. 3uring an analytical run( the sample is carried through the pre-column toward the analytical column. 8hen the compounds of interest ha$e cleared the precolumn( a $al$e arrangement switches the direction of the carrier gas flow so it flows through the 0tee0 connector to both columns. The components that ha$e already passed the 'unction continue through the analytical column to the detector( while compounds before the 0tee0 are flushed bac= out of the pre-column and $ented. %t is important to select the correct time to re$erse the flow through the pre-column( or compounds of interest may be lost or undesirable compounds may be dri$en through the analytical column. Identification and Integration of Peaks. 3uring this step a detector senses the presence and amount of compounds as they elute from the column. Table /+.6 lists characteristics of se$eral common types of detectors? some portable GCs feature additional detectors for specific applications. The instrument:s software compares each pea= as it elutes to the calibration data and shows the name( concentration le$el( and retention time of the compounds identified during calibration. Compounds that are detected( but which do not match compounds identified during calibration( are listed as 0un=nowns0 and often may be identified by the software by comparing the sample analysis results with other calibration results stored in the instrument:s memory or by scanning $arious compound libraries that may contain se$eral hundred compounds. The compound:s concentration is calculated from the area under its pea=( a step called pea' integration. #ome instruments can be programmed so there is a delay between when the first pea=s emerge from the column and when the compound identification and pea= integration begins. This feature( called the inhibit time, is helpful in reducing the amount of data generated when the initial( lighter molecules do not represent compounds of interest. Data Display and Management. The laptop computer and proprietary software stores and displays rele$ant data such as the sample chromatogram( calibration chromatogram( retention times( concentration( and operating parameters. 3ata management is critical with portable GCs because compound identification is based on the principle that when a specific column is maintained at a specific constant temperature and carrier gas flow conditions( the retention time of each compound is constant. Thus all the operating parameters (column type( temperature programming cycle( carrier gas flowrate( etc. must be stored along with the calibration data so that proper identification of pea=s in actual samples is achie$ed. )dditionally( the instrument must be recalibrated fre1uently( and so ade1uate data storage capability is needed to store the calibration and sample data. P rta$le GC I(str!"e(ts This section describes se$eral commercial portable GC instruments that illustrate features typically a$ailable with this category of instrument. Photovac Voyager Portable GC. The @oyager Bortable GC (;igure /+.J is designed for en$ironmental site characteri>ation and exposure monitoring. 8eighing
.19 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR T)BD< /+.6. Types of GC 3etectors Type ;lame ioni>ation detector (;%3 Brinciple Compounds 3etected ) stainless steel burner in which hydrogen )lmost all organics? response is is mixed with the sample stream? greatest to hydrocarbons? combustion air feeds in and diffuses decreases with increasing around the 'et (burner where ignition substitutions of other occurs. The current carried across the elements: A( #( Cl. 4ot gap of a platinum-loop collector sensiti$e to water( the electrode is proportional to the number permanent gases( and most of ions generated by burning the sample. inorganic compounds. 4ot as sensiti$e as many other detectors. Darge linear range. &esponse is relati$ely uniform from compound to compound. ) sealed E@ light source emits photons Arganics( some inorganics( with an energy le$el high enough to lower response to lowioni>e the compounds in the sample. %n molecular-weight a chamber exposed to the light source hydrocarbons. Can detect containing a pair of electrodes( ions aliphatic( aromatic( formed by the absorption of photons are halogenated hydrocarbons. dri$en to the collector electrode where a )rsine( phosphine( hydrogen current is produced that is proportional sulfide. #ensiti$e to water. 4o to the concentration. Darge linear range? response to methane. high sensiti$ity? selecti$ity can be <specially good for aromatic introduced by using different energy hydrocarbons. lamps. &esponse $aries from compound to compound. Etili>es a radioacti$e source such as G(64i to supply energy to the detector in the form of (6 radiation. %ntensity of the Compounds containing electron beam arri$ing at a collection halogens( cyano or nitro electrode is monitored. 8hen an groups? <C3 has a minimal electron-capturing species passes response to hydrocarbons( through the cell the intensity of the alcohols( and =etones. electron beam decreases( sending out an electronic signal. &esponse $aries widely from compound to compound. .ighly sensiti$e and selecti$e. Botential problems include excessi$e heat( which could $apori>e some of the source? 0aging0 of the coated foil( which must be replaced? gradual loss of the source:s acti$ity. using the built-in DC3 or by downloading to a computer in the field or office.+ The Bhoto$ac @oyager GC can be used to analy>e air samples( soil gas( or the head-space abo$e water or soil samples. Gaseous
Bhotoioni>ation detector (B%3
<lectron capture detector (<C3
/5 pounds( it is e1uipped with an internal refDllable carrier gas cylinder and rechargeable battery for independent operation for up to F hours. #ampling practitioners can $iew the chromatograms or tabular data
PORTA3LE GAS C4ROMATOGRAP4S *GCs.10 Figure 12.%. Bhoto$ac @oyagerM multicolumn configuration allows separation of up to ,* compounds in a single sample. (Courtesy of Bhoto$ac( %nc.
Figure 12.$. Bhoto$ac @oyagerM portable gas chro-matograph. (Courtesy of Bhoto$ac( %nc. samples can be in'ected manually by syringe( or sampled using a built-in pump and loop in'ection. Doop in'ections are ideal for fenceline( ambient( confined space( emergency response( lea= detection( and similar applications. #yringe in'ections are used for applications such as headspace analysis of waste streams( ground water( and soil extracts. The sampling practitioner can choose from a manual or continuous loop in'ection sampling mode. The instrument can be set to sample at user-defined inter$als( thereby pro$iding a time-history profile of concentration le$els for site-specific compounds. The @oyager uses two detectors: a photoioni>ation detector (B%3 operating at /*.J e@ for $olatile organic compounds (@ACs and an electron capture detector (<C3 . The <C3 is the most sensiti$e detector a$ailable for the analysis of elec-trophilic compounds such as chlorinated
hydrocarbons and other halogen-containing organic compounds. ) @oyager with a B%3 and an <C3 re1uires ultra>ero-or >ero-grade nitrogen carrier gas. The nitrogen must be II.IIIC pure and contain less than *./ ppm of hydrocarbon contamination. 8hen only a B%3 is used( the instrument can be run with nitrogen or >ero-grade air as the carrier gas. Di=e nitrogen( the air must be II.IIIC pure and contain less than *./ ppm of hydrocarbon contamination. The instrument employs an inno$ati$e arrangement of analytical columns( preprogrammed temperatures( and flowrates to optimi>e the separation of complex @AC mixtures found in specific industries. Ane precolumn and three parallel analytical columns (;igure /+.- ma=e up this configuration. Esing three separate columns allows separation of up to ,* compounds in a single sample. <xcellent compound resolution on at least one of the three column phases generally occurs. ) bac=fDushing feature can be used to reduce total analysis time and column contamination by pre$enting the hea$ier 0nontarget0 analytes from entering the analytical columns. The @oyager GC has a built-in total @AC (T@AC operational mode which allows a 1uic= screen of samples for the presence of @ACs. %n a T@AC run( the sample passes directly into the B%3 without going through the analytical columns. %f a preset alarm le$el is exceeded( a full GC analysis may be performed to determine
.82 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR which compounds are present. ) T@AC analysis is sent through the B%3 onlyHa T@AC sample cannot be run through the <C3. Broprietary software (#iteChartM is pro$ided with this instrument. The software sets up the preprogrammed parameters for different calibration and analytical runs (called assays) and is also helpful for data re$iew and printing of the data including chromatograms and tables of pea= $alues. <ach assay automates the setup of the instrument operating conditions and data reduction parameters pertinent to identifying and 1uantifying a predefined set of compounds. The preset operation parameters ensure the best separation and detection possible for the compounds in a sample. The @oyagers are e1uipped with preprogrammed assays to detect a set of target analytes for the following specific industries: en$ironmental (i.e.( the ,* compounds on the E.#. <B):s TA-/, priority pollutants list ? petrochemical! refining? rubber!plastic? pulp 9 paper? surfactants!sterilants? and latex polymers. %n addition( each instrument is furnished with a uni1ue assay dis= de$eloped from the setup and calibration performed at the factory to meet the user:s specified needs by running target compounds on that instrument and sa$ing the respecti$e retention times and pea= areas in the library. The sampling practitioner can also use the #iteChartM software to set up and store additional assays. The @oyager portable GC can be run in the field using a personal computer with #iteChartM( or using the =eypad on the instrument as long as the desired assay has been downloaded to the instrument from the computer using the #iteChartM software. The @oyager data logs e$ery completed analysis. Ep to ,* GC log entries can be stored in the instrument:s memory( which is sufficient for an F-hour day based an analysis e$ery /* minutes. T@AC runs occupy less memory than GC runs( so the de$ice will typically be able to store /* times more T@AC runs than GC entries. Ance the memory is full( the data may be downloaded or else deleted from memory so that additional runs may be performed. <ach GC record includes a complete pea= report and chromatogram. Ance data ha$e been downloaded to the computer( they can be re$iewed by scrolling through the list of completed runs( then selecting( analy>ing( and printing a specific chromatogram or data summary. Di=e all GC instruments( proper calibration is critical. 8hen a calibration run is performed( the data are stored in a library in the @oyager:s memory. The library contains the retention time( pea= area( and concentration of each target analyte. 8hen a standard( preprogrammed method is changed (e.g.( pressure or temperature change ( the retention times for the compounds will shift. ) new library then needs to be created to identify the target analytes by running the compounds of interest with the current method conditions and sa$ing the retention time in the respecti$e library. 8hile the manufacturer strongly recommends that the @oyager be calibrated using a calibration mix that contains e$ery compound in the column:s library( it is possible to calibrate it using a calibration mixture containing only a few of the compounds. Called a ratiometric calibration( the instrument performs a calibration with each compound in the calibration gas mixture and then calculates the approximate retention times and concentrations settings for the compounds that were not present in the calibration mixture. )fter a ratiometric calibration( the instrument:s compound library is updated to reflect the actual and calculated information. #ince the approximation may affect compound identification and the accuracy of the compound concentration reported by the instrument( a ratio-metric calibration is not considered as good as an actual calibration with a =nown standard of each compound of interest.
PORTA3LE GAS C4ROMATOGRAP4S *GCs.85 any manufacturers: columns can be used. The o$en can be operated at a constant temperature (isothermal or with temperature programming to increase temperature as the sample run progresses (up to +**KC for faster analysis( or analysis of $olatile organic compounds (@ACs and semi-$olatile organic compounds such as poly-nuclear aromatic hydrocarbons (B).s ( some pesticides( and plastici>ers in the same sample. Typical columns that are used include: Figure 12.&. .4E "odel GC-6// Bortable GC can analy>e gases( li1uids( and soil extractions using a $ariety of columns and detectors. (Courtesy of B%3 )naly>ers( DDC. &ac'ed Columns. /!,0( /!F0( or /!/J0 (micropac= +-6 meters in length with 6**-5** plates per meter. The typical pac=ing material is porous polymer( li1uid phase (/-6C on diatomite. Capillary columns. *.56-( *.6+-( *.+*-( *./5-mm column with li1uid phase bonded to the fused silica? a$ailable in fused silica-lined stainless steel with the li1uid phase bonded to the silica? efficiency O/***-6*** plates!m with typical length /5-6* meters. Sentex Scentograp P!US II. T'e Scen( tograph BDE# %%( from #entex #ystems( %nc.( is designed to operate as a portable unit or in a fixed location (;igure /+.I . %t is capable of analy>ing air( soil( and water samples with concentrations ranging from parts-per-trillion (ppt to percent (C le$els. This is accomplished by combining different ways of sample introduction with different types of detectors. #amples can be analy>ed by direct on-column in'ection( using a concentrator or using a sample loop./ The detectors offered are micro argon ioni>ation detector (")%3 ( argon ioni>ation detector ()%3 ( electron capture detector (<C3 ( thermal conducti$ity detector (TC3 ( and the photoioni>ation detector (B%3 . The )%3 is sensiti$e to organic compounds ha$ing ioni>ation potential of //.- e@ or lower. These compounds include the halomethanes and
HNU Model GC-311 Portable GC. T'is microprocessor controlled portable instrument (;igure /+.F can analy>e gases (ambient air( headspace( stac= samples( process gases( etc. ( li1uids (water( sol$ents ( and either headspace or li1uid extractions of solid samples such as soils. %t has a heated in'ector for manual in'ection of gases or li1uids and has dual detector capability chosen from six interchangeable detectors: Bhotoioni>ation detector (B%3 ( flame ioni>ation detector (;%3 ( electron capture detector (<C3 ( flame photometric detector (;B3 ( thermal conducti$ity detector (TC3 ( or far ultra$iolet absorbance detector (;E@3 . The instrument is pro$ided with .4E:s proprietary software called Bea=8or=sM for 8indowsN Chromatography #oftware for data management and control of the GC.6 )nalyses can be run in series with nondestructi$e detectors such as B%3 or ;E@3 or in parallel with the other detectors to impro$e or $erify compound identification. ) built-in concentrator!thermal desorber is a$ailable as an option for indoor air 1uality and fenceline measurements where $ery low le$els (ppb to ppt are to be measured. The instrument features a large o$en so
.86 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR of F hours: supply of calibration gas. There is also a calibration port that is used to calibrate from a sampling bag( headspace of an external container( or other external source at ambient pressure. The #centograph BDE# %% can use the following methods to identify and 1uantify components in samples: Esing current calibration data( which is based on direct calibration Peither single point or multipoint (up to 5 points Q with certified standards for up to ,F chemicals. 3uring analysis( the instrument compares the retention times obtained with those of the calibration run. 8hen there is a match( the name of the compound and the calculated concentration le$el is displayed on the monitor. Bea=s with no match are identified as 0un=nown.0 This method is the most accurate and is identical to that used in laboratory gas chromatographic analysis. Esing pre$ious calibration information stored in data files( which is similar to the pre$ious method with the exception that the calibration data is recalled from the system:s memory for comparison to the analysis data. ;or example( suppose a calibration run was performed under certain parameters and the $alues were stored in the instrument:s memory. %f an analysis is conducted at a later time under the same parameters( it is possible to recall the pre$ious calibration and compare it with that analysis. %f there is a match( the pea=s will be named and their concentrations will be determined. Esing a computer library search( which is based on the assumption that those relati$e retention times of compounds separated on a column remain unchanged( pro$ided that the operating conditions of the analysis are =ept the same. 3uring an analysis run( the system will first 0loo=0 for compounds
Figure 12.). The #centograph BDE# %% fieldportable GC unit. (Courtesy of %nficon( %nc. haloethanes( carbon tetrachloride( and /(/(/trichloroethane( which are poorly detected by other common field detectors. This detector is capable of detecting these compounds as well as other hydrocarbons down to ppb le$els. The ")%3 is a smaller( more sensiti$e $ersion of the )%3. %t is ideal for use with capillary columns and detects organic compounds to below / ppb le$el. The instrument can contain two detectors at any one time? howe$er( only one can operate at a time. The operating temperature can be set between 6* to /-IKC? a temperature abo$e 5*KC is recommended for optimum performance. The internal carrier gas cylinder is filled with argon (II.IIIC pure for the )%3 or helium (II.IIIC pure for the <C3( B%3( or TC3. The carrier gas cylinder will allow a minimum of F hours of operation and is easily refilled. %t is also e1uipped with an internal calibration cylinder( which supplies gas directly to the instrument:s internal calibration system. Calibration gas from the internal cylinder flows through a regulator directly to the sample loop or concentrator during calibration. The calibration cylinder is easily refillable and pro$ides a minimum
PORTA3LE GAS C4ROMATOGRAP4S *GCs.8. that were defined in the calibration run. 0Enmatched0 compounds are then screened using data stored in different internal libraries. The library search method is a con$enient procedure for analysis. .owe$er( library $alues must be chec=ed fre1uently in order to maintain their accuracy. The #centograph BDE# %% can contain se$eral libraries (i.e.( databases ( each containing up to ,F compounds. The instrument uses menu-dri$en software to control its operation( process its data( and store its chromatograms. The systems can be operated manually or set to analy>e and calibrate at chosen inter$als( storing the results on dis= or hard dri$e for future re$iew. ) detachable laptop computer controls the operation and pro$ides the data system. The proprietary #entex software operates the GC and collects( stores( and processes data. Typical (peration. The operation of any portable GC depends on the features of the instrument and the manufacturer:s instructions. ) typical operating se1uence for portable use of the #centograph BDE# %% is as follows/: /. @erify that the batteries are fully charged by charging o$ernight particularly after a prolonged period of nonuse. +. Turn on the carrier gas $al$e and the calibration gas $al$e (if the internal calibration cylinder is to be used at the calibration source . @erify that both gas cylinders are full by inspecting the pressure gauges when $al$es are opened. &efill cylinders if needed before field use. 6. %f calibration from an external source is desired( the internal calibration cylinder gas $al$e should be turned off. The instrument will automatically draw a sample through the external calibration port. ,. %nspect the column pressure using the column pressure gauge. )d'ust column pressure if necessary. Typical operating pressure should be +*-6* psi for pac=ed columns and F-/5 psi for capillary columns. 5. Connect the &#-+6+ connector from the instrument to the computer( turn on the computer and start the software program. The computer will automatically power the GC unit( initiate the start-up cycle( and display rele$ant parameters and prompts. J. #elect the calibration or analysis mode as appropriate. Change parameters( select features as re1uired( and manipulate data as prompted by the computer. -. 8hen using direct syringe in'ection of samples( use these guidelines: )as Samples. #ample $olumes up to +cc can be in'ected. ) gas-tight syringe should be used for handling the samples. The syringe needle should be ++-+J gauge with either a ++K be$el point or a side port tip. The $olume to be in'ected is dependent on the sample concentration. The higher the sample concentration( the smaller the sample in'ection $olume must be to a$oid o$erloading the detector. ;or sample concentrations between 5** and 5*** ppm( a sample si>e of *.5 cc or less should be used. %f sample concentration is un=nown( start with a smaller si>e in'ection. %ncrease the in'ection $olume to increase the analysis sensiti$ity. ;or the lower ppm range (/ to /*ppm ( an in'ection si>e of / cc can be used. Barts per billion (ppb analyses of gas samples would re1uire a sample in'ection of up to +cc. #i$uid Samples. The sample si>e is much less than that used for a gas
.87 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR sample in'ection( typically ,uD or less( depending on the sample concentration. The capacity of the syringe should range between luD and /* uD( and it should ha$e a ++-to +J-gauge needle with either a ++ c be$el point or a side point tip. F. )fter use( follow the computer prompts to shut down the instrument. 8hen the instrument is not in use( it should be connected to the charger at all times. P rta$le GC Mai(te(a('e a(, Use %n addition to the material already co$ered in this chapter( there are se$eral maintenance and use considerations for portable GCs. &outine maintenance in$ol$es steps such as: &eplacing in'ection port septum e$ery +-5 in'ections. &eplacing inlet filter approximately once!wee=( depending on sample dust content. Cleaning E@ lamp window as needed. &eplacing E@ lamp when needed. Cleaning in'ection port as re1uired. Conditioning column when changing column or if contamination is suspected. Burging internal carrier gas cylinder before shipping instrument or if cylinder becomes completely empty. )ny column can become contaminated with compounds ha$ing long retention times. %f contamination of a column is suspected( installing a new column is one way to chec=. Contamination may be pre$ented by using the bac=fDushing feature if a$ailable( or reduced by flushing the column with carrier gas for a period of time after e$ery analysis. .owe$er( a disad$antage of purging the column after each analysis is the time in$ol$ed since it will decrease the number of samples that can be analy>ed in a day. ;or a contaminated column( simple flushing may be used or ba=ing the column in a drying o$en at a temperature recommended by the manufacturer while passing nitrogen or another gas through the column. The ba=ing time and temperature depends on the type of column being cleaned. 8hen changing columns( a conditioning period is re1uired. %f the ends of the column ha$e been =ept capped during storage( the length of conditioning time is reduced. 8hen installing the column( a$oid touching the unprotected column ends as contamination may result. )lthough portable GCs ha$e extensi$e datalogging and data management capability( it is usually helpful to =eep a separate record of =ey information. ;igure /+./* shows typical information elements to be recorded for use of a portable GC instrument. %t is also important to consider the appropriate shipping regulations concerning compressed gases if a sur$ey is planned at a distant location. Generally( it is best to ha$e carrier gas and calibration gas cylinders shipped to the sur$ey location ahead of time or purchased locally( since there are many restrictions on shipping compressed gas cylinders. St ra#e Re:!ire"e(ts Broper storage of portable GCs is important and the re1uirements $ary( depending on how soon the instrument should be ready for use. ;or example( one manufacturer gi$es these storage guidelines+: "aintain a flow of carrier gas through the column to pre$ent contamination. ;or longer storage periods( connect the instrument to an external supply of carrier gas. 3o not allow the internal carrier gas cylinder to empty completely to
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PORTA3LE GAS C4ROMATOGRAP4S *GCs-
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Figure 12.1*. GC data sheet.
.81 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR pre$ent contamination of the internal cylinder and columns. %f the internal cylinder empties completely( it must be purged before refilling. The column must then be flushed( and the instrument must be allowed to warm up for 6* minutes. The baseline of the instrument must be allowed to stabili>e before it is ready for use. #tore the instrument in a location that is free of $olatile organic $apors and gases( with ambient temperature between 6+K; and /*5K;. %f the battery has been discharged( connect the instrument to the )C adapter and recharge the battery. ;or immediate a$ailability( the following steps are recommended: Dea$e the instrument turned on. Calibrate once e$ery +, hours. Connect the instrument to a carrier gas cylinder( or refill the internal cylinder e$ery J-F hours. Connect the instrument to the )C adapter when not in use. ;or a$ailability within 6* minutes: Turn instrument off. Connect it to an external cylinder of carrier gas. Connect it to the )C adapter. To use the GC( turn it on and allow a 6*-minute warm-up period. Then calibrate it before use. ;or a$ailability o$er a longer period: ;ollow the storage recommendations for 6*-minute a$ailability( but let the instrument stabili>e for at least /+ hours before calibration. This will result in optimum performance. NIOSH Method for Ethylene O !de By Port"#le GC Ane established method using a portable GC is 4%A#. Manual of Analytical Methods (4")" 4umber 6-*+,: Proced re F. #et up a portable GC with a B%3 using the following parameters: column R /.+ m x 6 mm A3 BT;<( pac=ed with Carbopa= B.T ,*!/** mesh. Carrier gas flow rate R /5ml!min. )lso assemble portable computer or integrator( battery charger( regulator( and any other peripherals necessary for indi$idual instruments. )llow the instrument to warm up and e1uilibrate for 6* minutes. I. Chec= the sampling e1uipment to pre$ent contamination. Ese different syringes for sampling and for standard preparation. %dentify each syringe with a uni1ue number. #egregate bags used for sample collection from those used for calibration standards. /*. Calibrate the GC daily in the field. Brepare bag standards by adding a =nown $olume of ethylene oxide to a =nown $olume of clean air in a bag. By adding a =nown $olume in S*.D to a specified number of liters of air( a =nown concentration in ppm will be created. *ote+ Because ethylene oxide is a flammable gas( the shipment of the compressed gas must comply with ,IC;& /-/-/-- regulations regarding shipment of ha>ardous materials. //. <$acuate a 5-D to /*-D bag completely by drawing the air out with a large /-D to +-D syringe. /+. 3raw clean air (or oxygen or nitrogen from a supply cylinder into the syringe for measured transfer into the bag. )lternately( if a clean air supply is not a$ailable( draw room air through charcoal sorbent into the syringe. &epeat until the bag contains 5 D of air. /6. )dd a =nown amount of pure ethylene oxide or standard ethylene oxide mixture to the bag by means
PORTA3LE GAS C4ROMATOGRAP4S *GCs.88 of a gas-tight syringe. Example+ Esing a gas-tight syringe( ta=e 5* uD from a cylinder of pure ethylene oxide and in'ect it into 5D of air to create a /*-ppm standard. )lternately( +** uD of a +-C $!$ ethylene oxide mixture (e.g.( FF!/+ w!w ;reon /+ and ethylene oxide can be added to the 5 D of air to obtain a /*.Fppm standard. /,. )llow the bag to e1uilibrate( with occasional =neading( for at least 5 minutes. /5. )naly>e ali1uots of $arious si>es to establish a calibration graph. ;or each point three replicate samples should be done. ;or example( using a high instrument attenuation (low sensiti$ity ( in'ections of *.+mD( *., mD( *.J mD( *.F mD( and /* mD( might be possible. These amounts would correspond to in'ections of +iiD( ,iiD( JiiD( FiiD( and %AT%D. An a more sensiti$e attenuation( in'ections of *.*+ mD( *.*, mD( *.*J mD( *.*F mD( and *./* mD would be typical. &esults will $ary from instrument to instrument( and from time to time on the same instrument. /J. Blot iiD of ethylene oxide $ersus pea= height or area if the GC cannot do this automatically. This plot should be a straight line. /-. Beriodically throughout the day( chec= the calibration by repeating some of these in'ections. %deally( each sample would be brac=eted( before and after( with in'ections of standards( although this situation is seldom practical. #ome GCs are capable of doing automatic periodic calibrations with programming. /F. Collect samples by drawing air from the contaminated area directly into a syringe or filling bags for an integrated T8) sample. /I. ;or syringe sampling( draw air directly into a gas syringe. Collect syringe samples by first purging a gastight syringe se$eral times with clean air to remo$e any residual ethylene oxide from pre$ious samples? then draw air into the syringe at the time and location of interest. %f larger syringe samples are desired( such as +* mD of air( it will be necessary to transfer some of the sample to the smaller syringe being used in the chromatograph. %t is essential that the si>es of all grab sample in'ections be the same if concentrations are to be compared. ) rubber cap placed o$er the end port of the larger syringe can ser$e as a septum for the smaller (5** uD syringe. +*. ;or integrated air samples for T8) determinations( a clean bag of plastic or other material must first be e$acuated. ) personal air sampling pump is used at the highest airflow a$ailable. +/. )ttach the plastic bag $ia tubing to the outlet of a personal sampling pump and pump air from the contaminated area into the bag at a rate calculated to fill the bag o$er the sampling period. This rate will be between +* mD!min and 5** mD!min. Terminate sampling before the bag is F*C full. The pump:s flow rate must be within T5C of the initial setting throughout the sampling period. ++. )naly>e the bag sample within + hours after completion of the sampling to minimi>e loss of analyte by adsorption and permeation as follows: ;ill a gastight syringe( purged se$eral times with sample( from the sample bag. Then empty it to the desired $olume( and in'ect that $olume into the chromatograph with a 1uic= firm motion. &ecord the number of the syringe. Ese replicate analyses to determine the repeatability of the analysis. %f no
.89 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR estimate of concentration is a$ailable( use an in'ection $olume /* uD to +5 ixD at a high attenuation to reduce the possibility of column and detector o$erload. 3epending on the results of this in'ection( larger $olumes and!or more-sensiti$e attenuations may be selected. /J. Calculate the concentration of eth-ylene oxide from the calibration graph (riD and the in'ection $olume (mD : uD(gas iiD ppm R--------R------HD gas mD I(ter&reti(# Meas!re"e(ts with the P rta$le GC )s noted pre$iously( it is possible for more than one compound to ha$e the same retention time( and in certain circumstances where un=nowns may be present( it will mean that a pea= appearing at or near a gi$en retention time is not /**C confirmation of a gi$en compound:s presence. .owe$er( if the instrument is operating properly( a lac= of pea=s will usually mean there are no compounds present at the detection le$el of the instrument. The best way to confirm the presence of a gi$en compound is to collect additional samples for analysis in the laboratory on a GC with two different columns( each of which is capable of resol$ing the mixture of interest and doing se1uential analyses. )s this is difficult to do in most portable GCs where the results are 1uestionable( bag samples should be collected and ta=en to a laboratory for analysis. The interpretation of a chromatogram re1uires the use of calibration reference data that ha$e been generated through testing. Sources o" #rror. 8hen using a GC for analysis( there are se$eral sources of error that must be understood and a$oided in order to yield accurate results. These include/+: Bea= integration errors that are due to problems in starting or stopping the pea= integration by the instrument or computer software. The potential problems include baseline noise( interfering (co-eluting pea=s( or excessi$e tailing of the pea=s of interest. These errors can occur somewhat randomly and cause different integrations for consecuti$e runs for the same concentration of a specific contaminant under the same operating conditions. Because of this potential for error( it is important for the sampling practitioner to re$iew the chromatograms for ob$ious errors and to reintegrate where necessary using different parameters to achie$e accurate results. #yringe in'ection techni1ues may cause a large 0trailing pea=0 on the chromatogram that is not due to a target compound. %f an in'ection pea= is obser$ed( it may be eliminated by setting the inhibit time one or two seconds longer than the retention time indicated for this pea=. #ampling errors occur when the analytical sample entering the instrument is different from the airborne composition and concentration that exists at the sampling site. This can be due to reasons such as nonstandard syringe sampling and in'ection techni1ue( contaminants not being completed des-orbed when a concentrator is used( or contaminants condensing or otherwise absorbing on the walls of Tedlar sampling bags or in sampling lines. Careful attention to sampling techni1ues( including the use of heated sampling lines and bags where needed( along with rigorous laboratory e$aluation of planned sampling techni1ues can help to identify and reduce sampling errors.
PORTA3LE GAS C4ROMATOGRAP4S *GCs.80
Figure 12.11. 3iagram of a typical mass spectrograph. (Courtesy of %nternational #ensor Technology.
)dsorption of contaminants of interest within the internals of the GC system can sometimes occur( especially when the concentration of contaminants in the sample is extremely low. %f this does occur( it often affects only the first few samples since there are generally only a limited number of ::absorption sites0 within the instrument( and the error resol$es once these sites are occupied. This type of loss can be seen by gradually increasing results when the same concentration samples are run repeatedly until the a$ailable sites are occupied. Ese of a heated GC system helps to minimi>e this type of error. 3etector response drift occurs when the effecti$e response of the detector changes o$er time. ;or example( for a B%3 the effecti$e E@ lamp intensity may change. This drift is a time-dependent phenomenon( and it is not as compound-specific as se$eral of the other types of error. ;re1uent calibration( and especially recalibration when the detector:s baseline response has changed by a certain amount (often /*C ( is a way to pre$ent this error. The calibration should be performed under similar temperature and humidity conditions as the actual sampling.
Monitoring $ecords. Chromatograms and information on the operating parameters and calibration should be retained as part of the record of the sampling. The amount of data that are generated by a GC instrument is $ery large( and so some systematic way to identify and store the rele$ant chromatograms and supporting information is critical. ;igure /+./* shows a typical sampling to form for recording supplemental information. GC%Mass Spectrop otometer Instruments. A GC!mass spectrometer (GC!"# is a GC instrument that is e1uipped with a special detector that passes the ioni>ed molecules emerging from the separation column through an electric field that focuses the molecules by atomic mass (;igure /+.// . <ach gas molecule has a specific mass number or weight. 8hen the molecules are ioni>ed in an electric field and then focused into an ion beam( the beam can be directed into a magnetic field that is perpendicular to the ion beam. The magnetic field causes the ions to scatter and deposit onto different collectors according to their mass number. The hea$ier molecules ha$e more =inetic energy and thus will be influenced less by the magnetic field than lighter molecules. )s a result( the hea$ier molecules impact the collectors that are toward the outside
.92 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR of the cur$ed detector. The ions reaching each collector plate are 0counted0 as electrical signals. "# sometimes pro$ides a better means of identifying specific compounds using a library of data de$eloped for the specific instrument than do other GC detectors. ) GC!"# is especially useful when compounds emerge at the same time from the GC column (co-elute despite efforts to ad'ust operating parameters to obtain good separation( or for identifying un=nown compounds since the spectrographic pattern of the un=nown pea=s can be compared to information in the built-in data library. GC!"# instruments ha$e long been used in the laboratory( but their use as portable field de$ices is relati$ely new. They gi$e the sampling practitioner new options( but are costly and complex to operate. They probably add the most $alue when cost sa$ings or other benefits result from ha$ing real-time information in the field and a GC or other( less complex Figure 12.12. The %nficon .)B#%T< is a portable GC!"# weighing 65 pounds that brings new capability to field instruments. (Courtesy of carrier gas and has an internal calibration gas cylinder. %t has se$eral built-in programs to ma=e field use more con$enient. Ance the sampling practitioner selects a method( the instrument automatically ac1uires and analy>es the sample. The instrument monitors critical parameters( thereby $erifying the tuning of the "# and mixing internal standards with the sample at the re1uired ratios. &esults can be shown on the instrument:s display panel and stored for later downloading to a computer. The instrument can be used in two modes5: #ur$ey mode where 'ust the "# is used to gi$e 1uic= 1ualitati$e and semi1uantitati$e results. This mode is good for screening samples( e1uipment lea= chec=ing( or fugiti$e emissions testing. 8hen concentrations exceed preset threshold le$els( an alarm sounds. )nalytical mode which combines the GC and "# techni1ues. This permits detailed analysis of samples( and it is good for follow-up when the instrument in the #ur$ey mode detects a compound of interest. Typical applications of the .)B#%T< include source testing for en$ironmental permits( ha>ardous waste site testing( and emergency response testing. %t is finding increasing use for response to terrorism e$ents? a third-party manufacturer ma=es a .)B#%T< 0simulator0 that is designed for training with the instrument without using the consumable supplies such as carrier and calibration gas.:/ IN$RARE% (IR) SPECTROPHOTOMETERS 8hen infrared (%& radiation is passed through a sample of gaseous molecules( the
instrument will not suffice. The .)B#%T< by %nfDcon (;igure /+./+ is a portable GC!"#. %t weighs about 65 pounds and contains many of the features discussed earlier for portable GC instruments such as temperature programming and an optional concentrator for $ery low le$el air samples. %t uses nitrogen as a
NFRARED *IRSPECTROP4OTOMETERS .95 gas absorbs some specific wa$elengths of the infrared radiation. This increases the energy of the gas molecules( and so their $ibration or rotation increases. %& generally is that portion of the electromagnetic spectrum from --* nm to /*** 'am. %n %& spectroscopy( the term ,a!e number is also used This is the number of wa$es in one centimeter and is the reciprocal of the wa$elength( so %& ranges from about /+(I** cm/ to /* cm0/. Enli=e B%3s and similar ioni>ation detectors( the energy of the %& source is not high enough to cause ioni>ation of the gas molecules. %nstead( this energy transfer from the infrared radiation to the gas molecules can be seen as either (a increased energy (temperature in the gas molecules compared to molecules that ha$e not been exposed to the %& radiation or (b decreased intensity of some wa$elengths of the %& radiation that is transmitted through the gas sample. Two characteristics ma=e %& a good method of identifying and measuring the concentration of certain compounds: %& absorption spectrum is uni1ue to each gas or $apor molecules so %& can be a fairly specific detection method. Table /+., shows the %& absorption bands by chemical group and Table /+.5 lists the absorption wa$elengths for chemicals typically measured using %& technology along with the lower detection limit. The amount of %& absorbed is directly related to the number of the gas molecules in the sample which gi$es a good measurement of concentration. %ncreasing the length of the %& path through the sample allows measurement of low concentrations. %nternal mirrors are generally used to increase the path length to /* meters or more a sample cell of reasonable dimensions. )lthough the absorption spectrum is uni1ue for each chemical( care must be TABLE 12.#. Specific nfrare+ Absorption Ban+s )bsorption Grouping Band (Sim )l=anes C.6HCH( HC.+R 6.65-6.J5 )l=enes HC.RC.+ 6.+5-6.,5 )l=yne HCRCH 6.*5-6.+5 )romatic 6.+5-6.65 #ubstituted aromatics J./5-J.65 )lcohols HA. +.F*-6./* )cids HCAA. 5.-5-J.** )ldehydes HCA. 5.J*-5.I* Uetones ,c-o 5.J*-5.I* <sters HCAA& 5.-5-J.** Chlorinated HCHCl /+.F*-/5.5* Source+ 4%A#.: The ndustrial En!ironment, ts E!aluation " Control.
ta=en to select the optimum wa$elength for detection. ;or example( Trichloroethylene exhibits three absorption maxima (;igure /+./6 which occur at /*.5F( //.--( and /+.-F 'am. Theoretically( any one of these could be used to detect this compound( but the /*.5Fum pea= o$erlaps with ;reon-//6N and so is not suitable if ;reon could be present( and the /+.-F-um pea= o$erlaps with water $apor pea=s. Therefore the //.---um pea= is usually the best for trichloroethylene measurement. %& instruments $ary widely in complexity and functionality. #impler de$ices are dedicated to a single contaminant( while more complex instruments can measure many compounds by scanning the %& spectrum and applying sophisticated mathematical analyses to the raw data. )s an illustration( an %& at ,.6 'am is commonly
.96 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR TABLE 12... Typical Analytical /a0elengt' an+ 1inimum 2etectable Concentration for 3 nstruments Compound )cetaldehyde )cetic acid )cetone )cetonitrile )cetophenone )cetylene )cetylene tetrabromide )crylonitrile )mmonia )niline Ben>aldehyde Ben>ene0 Ben>yl chloride Bromoform /(6-Butadiene Butane Butyl acetate V-Butyl alcohol Carbon dioxide Carbon disulflde Carbon monoxide Carbon tetrachloride Cellosol$e acetate Chloroben>ene Chlorobromomethane Chlorodifluoromethane Chloroform Cresol Cumene Cyclohexane Cyclopentane 3iborane m-3ichloroben>ene o-3ichloroben>ene p-3ichloroben>ene /(/ -3ichloroethane /(+-3ichloroethylene 3ichloroethyl ether 3iethylamine 3imethylacetamide 3imethylamine 3imethylformamide 3ioxane <nflurane <thane <thanolamine <thyl acetate <thyl alcohol <thyl ben>ene <thyl chloride 8a$elength (Sim I.+J F.-+ F.,F I.JF /*.-* 6.*5 F.II /*.J/*.I5 I.56 F.5F I.I6 I.5, F.IJ //./* /*.,* F.66 I.-* ,.-+ ,.-* ,.-J /+.-J F.FI I.,* F.6I I.+* /6./+ F.FF I.I* 6.,/ //.,* 6.F6 I.,/6.55 I.6* I.5* /+.6* I.*5 F.II /*./* F.-I I.6J I.*J F.IJ /+.+* /+.I6 F.6+ I.JI.I* /*.5* "inimum 3etectable Concentration (ppm /./ *.6 *.J -.J *.6 /.J /.+ *.J *.5 *.+ *.6 +.+ +.5 *., 6.I 5./ *.J *.6 /*.+ ,.F +./ *./ *.6 *., /.5 /./ /./ *.+ +.6 *.I.* *.J *.6 *.J +.5 *., 5.6 *.*I /./ *., /.+ *.+ *.6 *.*6 /*.J +.I +./ +.6 6.* 6.,
NFRARED *IRSPECTROP4OTOMETERS .9. TABLE 12... Continued Compound <thylene <thylene dibromide <thylene dichloride <thylene oxide <thyl ether ;ormaldehyde ;ormic acid ;reon // ;reon /+ ;reon /6B/ ;reon +/ ;reon //+ ;reon //6 ;reon //, .alothane .eptane .exane .ydra>ine .ydrogen cyanide %soflurane %sopropyl alcohol %sopropyl ether "ethane "ethoxyflurane "ethyl acetate "ethyl acetylene "ethyl acrylate "ethyl alcohol "ethylamine "ethyl bromide "ethyl cellosol$e "ethyl chloride "ethylene chloride "ethyl iodide "ethyl mercaptan "ethyl methacrylate "orpholine 4itroben>ene 4itromethane 4itrous oxide Actane Bentane Berchloroethylene Bhosgene Bropane Bropyl alcohol Bropylene oxide Byridine #tyrene 8a$elength (Sim /*.-* F.JF F.66.6* I.*6 6.5J I.6J /*.IJ I.6* F.5, I.5* I.I* F.-* F.J/+.,J 6.,* 6.6I /*.J6.*6 F.F, F.I, I./+ -.-* /+./* I.6.* F.5I.-* 6.6J -.J* I.J+ /6.5I /6.,6.6J 6.6F F.F* I.+* //.I, 6.6,.JF 6.,* 6.6I //./* //.IF 6.6I.J* /+./J I.I* //./* "inimum 3etectable Concentration (ppm *.5 *.J /.6 *.+.F *.5 *.+ //.+ *./ *., +.6 /+.F 6., /.*.6 6.5 6.I *.J /.*.*, /.5 ,./ /.* *.+ +.6 +.* *./ *.- /.I +.6 *.6 6.* /*.* /.F /.5 /.* *.*.I ,.5 *., *.6 ,.J *.+ *./ J.5 *.F /./ F.J *.5
.97 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR TABLE 12... Continued Compound "inimum 3etectable Concentration (ppm /.I #ulfur dioxide I.** *.*+ #ulfur hexafluoride /*.F* /., /(/(+(+F.J* *.J Tetrahydrofuran I.,* I.+ Toluene /6.FI 6.I Total hydrocarbons 6.6I /.+ /(/(/ -Trichloroethane I.6I *.I /(/(+-Trichloroethane /*.I* *., Trichloroethylene /*.F, *./ @inyl acetate F.,+ *.F @inyl chloride //.6* *.6 @inylidine chloride I.,* +.* Wylene /6.+* 0 "inimum detection le$el exceeds current permissible exposure standard? therefore( recommended for gross lea= detection only. Analytical ,a!elength+ The analytical wa$elength is usually the strongest band in the spectrum that is free from interference due to atmospheric water and carbon dioxide. The listed wa$elengths are approximate. %f more than one %&absorbing material is present in the air in significant concentration( the use of another analytical wa$elength may be necessary. Minimum detectable limit+ The concentration that would produce an absorbance e1ual to twice the pea=-to-pea= noise in a typical portable %&. 8a$elength (Sim
Figure 12.1". %nfrared spectra of trichloroethylene. (;rom The ndustrial En!ironmentH ts E!aluation " Control, 4%A#.( Cincinnati( /I-6( p. +6,. used to measure carbon dioxide (C*+ le$els during indoor air 1uality (%)L studies and in the brewing( food processing and mining industries. %n %)L in$estigations an increase of C*+ abo$e the ,**-5** ppm in normal ambient air indicates that there is too little outside air being introduced in the occupied space for the number of people present. %n breweries( C*+ is produced as part of the fermentation process( and le$els may exceed acceptable exposure le$els in enclosed areas around $ats. ;igure /+./, shows a typical infrared instrument that pro$ides continuous autoranging detection of C*+ from le$els /* ppm to JC by $olume (J*(*** ppm and features pea=!hold memory( an internal sampling pump( and optional datalogging. ) dedicated %& instrument is also $ery good for measuring carbon monoxide (CA since there is little inference by other gases at ,.J 'am.
NFRARED *IRSPECTROP4OTOMETERS .9/ ;igures /+./5 through /+./- show different %& instrument configurations.- ;igure /+./5 is a basic layout with a single cell. %n some designs the sample is allowed to diffuse into and out of the cell rather than ha$e discrete inlet and outlets for a pump-dri$en system. This configuration has no way to ad'ust for possible drift in the %& source or detector. ;igure /+./J is a single cell configuration with two detectors. The acti$e filter!detector is chosen to measure the compound of interest( while the reference filter!detector is selected to ignore the target compound. %n actual operation the reference side pro$ides the >ero point while the acti$e side pro$ides the signal for measuring concentration. This arrangement ad'usts for changes in the %& source( and it also has the ad$antage of doubling the effecti$e path length since the %& beam tra$els to the mirror and then bac= to the detectors. ;igure /+./- shows a popular design with two cells. ;or instruments dedicated to a single chemical( the reference cell can either (a contain pure target gas and ser$e as the baseline for total absorption or (b contain pure reference gas (such as nitrogen and ser$e as the >ero baseline. ;or instruments that measure more than one gas( the reference cell is filled with a pure reference gas. ) chopper( which is a dis= with slots in it( alternately allows the light beam to pass through the sample and reference cells to the single Figure 12.1.. 3iagram of a simple ;or infrared detector. (Courtesy of all %& %nternational #ensor Technology. instruments the type of detector is important to measuring low le$els of Figure 12.1#. %nfrared-based carbon dioxide monitor pro$ides auto-ranging detection of le$els from lAppm to J*(***ppm. (Courtesy of %ndustrial #cientific Corporation.
Figure 12.1$. 3iagram of a two-detector infrared detector configuration. (Courtesy of %nternational #ensor Technology.
.91 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR
Figure 12.1%. 3iagram of a two-beam( single detector with chopper (Courtesy of %nternational #ensor Technology. used test gases such as sulfur hexaflu-oride (#;J . Emergency 1esponse Analysis. 3etercontaminant. ) $ariety of designs exist that are mining airborne le$els of ha>ardous spills based on measuring temperature rise as the %& and releases and ma=ing realtime decisions beam hits the detector(s or as the temperature regards personal protecti$e e1uipment for of the gas sample in the sample cell increases responders( boundaries of 0safe0 >ones and due to %& absorption. 3ifferent approaches the need for community e$acuation or include: (a thermoelectric detectors or shelter-in-place. thermisters that directly con$ert heat into an electrical signal (b microfDow sensors or a #ea' detection. )round e1uipment diaphragm between the detectors in the handling ha>ardous chemicals( such as reference and sample cells to measure the medical anesthetic gases or process units( small decrease in pressure in the detector as part of routine operations or pre$enti$e chamber due to absorption of the %& radiation maintenance. transmitted through the sample cell. Ane no$el approach is called a photo-acoustic detector( IR I(str!"e(ts f r Meas!ri(# Ma(% Gases which uses a sensiti$e microphone to measure a(, Va& rs the increase in pressure within a fixed sample %nfrared instruments with the capability of cell due to the absorbed %& radiation. measuring the concentration of many gases and Typical applications for %& instruments in $apors differ from the configurations shown in addition to en$ironmental measurements and ;igures /+./5 through /+./- in that they need a occupational exposure monitoring include: way to $ary the wa$elength of the %& radiation directed through the sample cell to match the ndoor Air -uality Studies. "easurements absorption spectra of target compounds. This for compounds such as C*+( CA( can be achie$ed by a $ariable wa$elength filter formaldehyde( or organic $apors. or by ha$ing se$eral fixed-wa$elength band .ume /ood0Tracer )as Analysis. Ane of pass filters in the de$ice. %n addition( these the standard tests for laboratory hood F instruments need a means to $ary the path performance is to release a tracer gas length using ad'ustable mirrors or another within the hood under different operating means in order to achie$e ade1uate sensiti$ity conditions and monitor the hood perimeter for different compounds and also increase the for lea=age bac= into the laboratory. ) measurement range for certain compounds. portable %& can measure commonly
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NFRARED *IRSPECTROP4OTOMETERS .98 also be operated from the alphanumeric =eypad. The de$ice weighs +, pounds( and battery ser$ice life is approximately four hours. Because %& de$ices are sensiti$e to ambient temperature( relati$e humidity (&. ( and atmospheric pressure( three different operating conditions are specified: &eference operating conditions( within which the influence of temperature( &.( and pressure is negligible( is +6 T +KC( 5* T /*C &.( and /,.--/5.6 psi. 4ormal operating conditions( within which the de$ice is designed to operate at the specified accuracy( is 5-,*K C( 5-I5C &. (noncondensing ( and /+.5-/5.6 psi. 4ormal operati$e conditions( within which the de$ice can be sub'ected without permanent impairment of operating characteristics( is /-5*KC( *-/**C &. (noncondensing ( and //.J-/5.Ipsi. "aximum temperature for intrinsically safe models is ,*K C. &ourier 'rans"orm In"rared (&')I$* +nal,-er. The ;ourier transform infrared (;T%& de$ice is a more complex and powerful type of analy>er when compared to a simple %& analy>er discussed abo$e. The ;T-%& uses a unit called a "ichelson interferometer to measure the absorption of %& radiation at different wa$elengths. The interferometer (;igure /+./I functions as follows-: &adiation from the %& source is split into two e1ual beams in the beam splitter. Ane beam continues on a straight path to a mo$ing mirror( while the other beam is deflected at an angle to a fixed mirror. 8hen the two beams recom-bine after being reflected from the mirrors( they undergo a process called interference. %f both reflecting mirrors are exactly the same distance from the beam splitter( both beams will be in phase with each other and the resulting recombined beam out of the unit will ha$e the maximum amplitude. The
Figure 12.1&. The "%&)4 #apph%&e portable infrared instrument. (Courtesy of Thermo <lectron Corporation. MIRAN SapphIRe Analyzer. O(e of the most common %& de$ices for field measurements is the "%&)4 #apph%&e series of instruments (;igure /+./F from Thermo <lectron Corporation. The #apph%&e )naly>er is a$ailable in three models with gas calibrations from one to o$er /** gases. %t is a microprocessor-controlled single-beam instrument that utili>es interacti$e programming to prompt the sampling practitioner through a$ailable options and functions.: The %& wa$elength is $aried using a $ariable filter from -.- to /,./ 'am( along with se$en fixed band-pass filters: /.F( 6.6( 6.J( ,.*(,.+(,.5( and ,.- 'am.The sample is drawn into the +.+6-D sample cell by an internal pump at a rate of /5 D!min. The path length can be $aried between *.5 and /+.5 m. )fter the instrument is powered up and stable( sample analysis time is +* seconds minimum and 6 minutes maximum. The response time is approximately /F seconds to reach I*C of final reading. The #apph%&e has a digital readout of concentration in $arious units (ppm( percent( and mg!m6 or absorbance units ()E . There is a &#-+6+ connection to use a personal computer for operating the instrument and downloading data( although the de$ice can
.99 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR
Figure 12.1). 3iagram of a ;ourier transform infrared (;T-%& analy>er. (Courtesy of %nternational #ensor Technology. position of the mirror is computer controlled? a laser precisely measures the position of the mirror. ;or each fre1uency( as the mo$ing mirror mo$es through its cycle( the interference pattern of the recombined beam will be from totally in phase to totally out of phase to totally in phase again. Esing a beam chopper( the recombined beam alternati$ely passes through the sample cell and the reference cell to reach the detector. The computer collects the data from the detector( which is a complex measurement of all the phase relationships at a gi$en time( to produce an interfero-gram, which shows the intensity of the infrared radiation as a function of the displacement of the mo$ing mirror. ) sophisticated computer program applies a mathematical ad'ustment( called a ;ourier transform( to the interferogram to determine the identity and concentration of the gases that are present. ;or a multicompo-nent analysis( the computer retrie$es calibration data in the computer:s library and tries to calculate a spectrum that is a close match to the actual sample spectrum by mathematically $arying the concentration of each component. 8hen it achie$es the best possible fit between the calculated spectrum and the sample spectrum( it reports the results.
Figure 12.2*. Temet Gasmet 3W-,*/* portable ;T-%& analy>er ready for field use. (Courtesy of Temet %nstruments Ay( .elsin=i( ;inland. The G)#"<TM 3W-,*/* from Temet Corporation is a ;T-%& de$ice designed for onsite measurements (;igure /+.+* . %t incorporates ad$anced hardware and software to pro$ide a portable high-speed identification and 1uantification of multiple gaseous compounds simultaneously and accurately( with results a$ailable in seconds( for applications such as:
<n$ironmental emissions monitoring Luality control 8or=place air monitoring The instrument can analy>e up to 5* compounds simultaneously. The sample is drawn into the /.*--D sample cell by an internal pump at a rate of l-5D!min. ) filter (+ 'am is re1uired on the sample line to protect the optical parts from particulate matter. The sample cell has a multipass( fixed path length of /.+( +.5( 5.*( or I.Fm. )fter the instrument is powered up and
NFRARED *IRSPECTROP4OTOMETERS .90 stable( sample analysis time is /+* seconds or less( depending on the gas flow and measurement time. )n external personal computer controls the instrument. The proprietary software( called C)DC"<TM( is used to compute the concentrations and error limits of the different components present in the sample gas. The reference spectra needed for the analysis are stored on the fixed dis= of computer and are loaded from the library when used in the analysis of an un=nown sample. )n &#-+6+ connection connects the computer to the instrument./* The 3W-,*/* uses an interferometer called the Temet Carousel interferometer. The Carousel interferometer is rugged and withstands the demanding en$ironmental conditions of nonlaboratory en$ironment. The Carousel interferometer modulates the infrared radiation coming from the infrared source( as described abo$e. The modulated light passes through the temperature-controlled sample cell. The transmitted infrared radiation is detected by a thermoelectrically cooled detector. %t is recommended that the instrument is operated in the following en$ironmental conditions: *-,*K C operating temperature in short-term use /5-+5KC operating temperature in long-term use GI*C relati$e humidity at +*KC( noncondensing The ambient temperature of the use location should be stable. Temperature fluctuations of a few degrees Celsius can in some cases affect the analysis results and the accuracy of the measurements decreases. The influence of the temperature fluctuations can be eliminated by remea-suring the bac=ground (>ero spectrum at the existing ambient temperature. )dditionally( the use location should be free of strong $ibrations. The standard case is not explosion-proof( and so the 3W-,*/* must not be used to measure explosi$e gas mixtures or gases that might form an explosi$e gas mixture with the ambient air. !dvantages and "imitations. The ad$antage of %& is that units can be purchased that are specific for gi$en chemicals( or tunable units can be purchased and used for many different compounds with a minimum of setup time. %n the field they are easy to use and pro$ide stable operation. 3etection limits depend on the absorption coefficient of the compound at a gi$en wa$elength or fre1uency. The limit of detection for many compounds is in the range of lppm to +*ppm. "aximum concentrations are commonly in the low percent range. The usefulness of %& analy>ers for monitoring complex mixtures is limited because o$erlapping pea=s produce an additi$e response( ma=ing concentrations appear higher than they actually are. ) wa$elength that is relati$ely uni1ue to a chemical is selected for monitoring and ideally there should be no others that interfere. .owe$er( this is often not the case( and a re$iew of the chemicals li=ely to be present during monitoring should be done to assure that an interferent will not be a problem. %nterferences depend on the contaminant being measured. ;or example( chlorinated hydrocarbons will all absorb at approximately the same wa$elength. This problem can be partially minimi>ed by ta=ing measurements at a secondary absorption wa$elength for substance confirmation. ) primary interferent is water $apor. The effect of water $apor can be minimi>ed by passing the air sample through silica gel or a similar drying agent( maintaining constant humidity in the sample and calibration gases by refrigeration( saturating the air sample and calibration gases to maintain constant humidity( or using narrowband optical filters in combination with some of the other measures.// Carbon dioxide can also be an interference(
.02 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR although its effect at concentrations normally present in ambient air is minimal. )ccording to the )merican #ociety for Testing and "aterials ()#T" ( -5* ppm of carbon dioxide may gi$e a response e1ui$alent to *.5 ppm carbon monoxide.// #ome instruments ha$e microprocessors that allow them to correct to some degree for interferences( and the sophisticated mathematical algorithms in a ;T%& de$ice can correct for many interferences. Calibration. A multipoint calibration is re1uired when an analy>er is first purchased( when the analy>er has had maintenance that could affect its response characteristics( or when the analy>er shows drift in excess of specifications as determined when the >ero and single point calibration is performed. ) >ero and single point calibration is re1uired before and after each sampling period( or if the analy>er is used daily. The fDowmeter should be calibrated as well when the analy>er if first purchased( when it is cleaned( and when it shows signs of erratic beha$ior.// Ance calibration plotting cur$es are prepared for a gi$en compound( air concentrations can be obtained by measuring the absorbance at the analytical wa$elength and reading the concentration from the point where the absorbance intersects the cur$e. "ost calibration cur$es of this type will ha$e some cur$ature( so it is best to use a plot prepared with three or four data points( rather than using a single-point and a straight-line approximation. %f only a single calibration concentration is a$ailable( it may be used? the measurements will be most accurate near this concentration point and less accurate at other $alues due to cur$ature. "anual calibration of most long path-length %& instruments is done using a closed-loop system. #mall amounts of contaminant (typically microliters are added to a fixed $olume sample chamber (generally +-J D without measurably affecting the pressure of the system( creating a =nown concentration in the parts per million (ppm range. Eser calibrations re1uire considerable practice in using the closed-loop system and becoming familiar with the instrument in order to consistently generate reliable accurate calibrations. Calibration of %&s can also be done using =nown concentrations in gas cylinders. Care must be ta=en during calibration of %&s( because these are nondestructi$e instruments? thus( any contaminant that enters the instrument will come out essentially unchanged( allowing the user to be exposed to the calibrant gas. The exhaust from the analy>er should be $ented to a laboratory hood or other exhaust to remo$e contaminant( both during calibration and analysis( to pre$ent buildup in the surrounding en$ironment. The first step in setting up an %& analy>er to measure a gas is to select the wa$elength and path length. 8a$elengths are chosen to maximi>e analytical sensiti$ity while minimi>ing interferences from other $apors commonly present in the wor=place or atmosphere where this contaminant is typically found. ;or example( if measuring styrene $apor in a chemical plant where acrylonitrile butadiene styrene ()B# polymer is manufactured( then /(6-butadiene is li=ely to be present. #ince this compound absorbs at the most fre1uently chosen analytical wa$elength for styrene (ll.lAum ( an alternati$e wa$elength must be chosen. An the other hand( if doing a sur$ey in a fiberglass boat hull construction facility where acetone is commonly used as a cleaning sol$ent for styrene( the acetone $apors would not be a concern as they are not li=ely to ha$e any absorption pea=s at wa$elengths that would interfere with styrene. #ince ambient air always contains water $apor and carbon dioxide( the analytical wa$elengths selected must reflect this ma=eup. #ome gases ha$e a limited number
INFRARED *IRSPECTROP4OTOMETERS .05 of possible analytical wa$elengths( and occasionally a wa$elength must be chosen where water $apor can interfere. This situation is associated with the 5- to F-um region where strong water $apor absorbance occurs. To reduce the interference of any water $apor( the instrument should be 0>eroed0 with air that has about the same humidity as the sample. %f an %& is o$erloaded from being exposed to too high a concentration( inaccurate calibrations and negati$e or suppressed readings at certain concentrations can result. %f the absorbances for any of the calibration standards go abo$e one absorbance unit( switch to a shorter path length or use a wea=er absorption band. There are many compounds for which %&s can be used. %n the case where the instrument has not already been set up to monitor for a gi$en compound( the manufacturer can often pro$ide information to select appropriate wa$elengths and path lengths for setting up %&s to monitor many different gases and $apors. 8hen the path length in a $ariable path length instrument is changed( the instrument should be recalibrated. Closed-#oop Calibration for the 1. 8hen using the closed-loop techni1ue( the user introduces pure samples through a septum with a li1uid or gas syringe. The sample is circulated through the system by means of the closed-loop pump. Esing the closed-loop system for the calibration of organic compounds with low $apor pressures may result in errors due to adsorption on the walls of the closed-loop system. The results of using a calibration cur$e based on these data would be to o$erestimate concentration during sur$eys. Therefore( e$en though closed-loop calibration systems are not recommended for compounds with $apor pressures less than /5mm.g (+5KC ( from the standpoint of using the instrument the errors may not be significant in certain types of sur$eys./+ Proced re /. 3etermine the sample $olume re1uired for the desired concentra tion limit. ;or gases the $olume to be in'ected is calculated using .i ppm R H 23 where 2i 4 $olume of gas to be in'ected( 23 4 $olume of closed-loop calibration system. ;or li1uids (at atmospheric pressure and +5KC the $olume to be in'ected is calculated using @i(d ( +,.,5 xlA6 ppm R-----------------M23 where 2i is the li1uid sample $olume in uD( d is the li1uid density in g!mD( M is the molecular weight( 23 is the $olume of closed-loop calibration system in D( and +,.,5 x /*6 is the number of uD of $apor per millimole of analyte at normal temperature and pressure (4TB . +6. %ntroduce clean air into the sampling chamber using a >ero air cylinder or room air drawn through a >eroing cartridge. +,. Connect tubing from the 0out0 connector of the closed-loop pump to the input port of the analy>er. Connect tubing from the 0in0 connector of the pump to the 0cal port0 connector of the analy>er. Turn the sample $al$e to the 0calibrate0 position. +5. Turn on the closed-loop pump. +J. %n'ect the 1uantity of calibrant gas or li1uid needed to fill the sample cell with the desired concentration. %n'ect e1ual increments to co$er a full range of concentrations. ;or example( if the maximum concentration is +** ppm(
.06 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR and the number of calibration points is to be fi$e( then each in'ection should increase in concentration by ,*ppm. ;re1uently replace the sili-cone rubber dis=s( called septa, used in the in'ection ports of closed-loop calibration systems. )fter a number of in'ections they may not reseal properly. +-. ;or each concentration( input the le$el into the instrument:s memory or otherwise set the 0span0 control (depending on the specific instrument . #ome instruments automatically fit a calibration cur$e to the data points. +F. ;or instruments with a 0general purpose0 scale (not mar=ed in ppm ( prepare a plot of meter reading $ersus concentration( with meter reading on the y axis and concentration on the x axis. En=nown concentrations can then be found using this cur$e and the meter reading. +I. ;ollowing calibration with each chemical( flush the closed-loop system and cell with clean air or nitrogen. The microprocessor capability of many instruments has simplified calibration in that certain parameters are programed into the instrument at the factory to allow for an electronic calibration chec=. The internal electronic calibration system often allows for field calibration without the need for calibration gas( which is sufficiently accurate for performing screening samples. )lthough this automatic (factory-pro$ided calibration sa$es time( it is not as accurate a calibration with a standard. &ield /peration. There are three primary types of sampling modes for %& analy>ers: bag sampling( lea= or fugiti$e emissions testing( and continuous monitoring. %n bag sampling( discrete breathing >one( area( or process samples can be collected in bags as described in the chapter on sample collection de$ice methods for gases and $apors (Chapter J using personal sampling pumps. The flow rate of the sample pump is not critical( as long as it is constant o$er the duration of the sample. ;ollowing sample collection( the bag is transported to the location of the %& analy>er where it is connected to the inlet of the sample cell. )n internal or auxiliary pump pulls the sample from the bag( through the sampling chamber( where it displaces the ambient air. 8hen the instrument:s response to the sample in the bag reaches a maximum( a reading is ta=en. The concentration of the contaminant can be determined from comparing the plot of instrument response $ersus the calibration cur$e concentrations( or directly from the readout if it is in ppm. ) similar application is to collect exhaled breath in bags and analy>e it on the %&. Bags can also be analy>ed to identify the presence of un=nowns on %&s with scanning capabilities. The scan of the un=nown atmosphere is compared with a scan of contaminants expected to be present to see if any unidentified pea=s are present. The instrument should generally be connected to a personal computer to manage the data during this analysis. 8hen sampling in situations where the atmosphere is un=nown( one techni1ue is to operate the %& at 6.,'am (the C-. bond stretching fre1uency using the maximum possible pathlength. %n the field( the response under these conditions should be reported as e1ui$alents of whate$er compounds ha$e been used to calibrate the instrument o$er the desired concentration range using the closedloop method./6 %n sur$ey instruments designed to detect lea=s( an extended sample probe of up to J feet in length made of inert tubing with a dust filter attached is used to ma=e spot measurements at many different locations( such as door seals( sumps( lines( and fittings. %f the filter becomes clogged( the sampling
NFRARED *IRSPECTROP4OTOMETERS .0. flow rate will decrease( resulting in a slower instrument response. &eplace the filter cartridge when the response time has increased noticeably( or after ,** hours of use. %n continuous monitoring( the instrument is stationed to collect samples at a location of interest. ) pump continuously draws sample into the sample cell( and the absorbance is continuously displayed on the instrument readout and stored in a data logger for printout later. %f measurements exceed the range for which the instrument was calibrated( it must be remembered that the response of %& analy>ers is not linear o$er the total range of the instrument( particularly at the ends of the scale? therefore( extrapolation past calibration points is not ad$ised. %f much higher concentrations than anticipated are identified( monitoring may need to be repeated following calibration at higher concentrations. %f the process being monitored is a constant operation with little $ariation( readings can be ta=en with the monitor e$ery 6* minutes. %f the process is $ariable( it may be necessary to ta=e the readings as often as $ery 5 minutes or continuously as described abo$e. %n compliance sampling with an %& de$ice( calibration should be done using either a premixed gas in a cylinder or the closed-loop calibration system rather than relying solely on the internal calibration system. ;or personal sampling( Tedlar gas bags capable of collecting a minimum of JD and personal sampling pumps e1uipped with exhaust ports are needed. Care must be ta=en to assure that sufficient air is collected to ade1uately purge the sample cell during analysis. %n certain en$ironments( a drying tube( Teflon sampling line( par-ticulate filter( or >ero gas filter may be necessary. %n general( where ambient air is drawn directly into the instrument all sampling should be done with the sample hose and particulate filter attached to pre$ent dust and particulate matter from entering the cell and accumulating on the mirrors and windows( thus interfering with the performance of the instruments by increasing bac=ground le$els. %&s should be used outdoors with great care because cooler temperatures and humidity can cause condensation on the mirrors and windows. %f the instrument has been in a cold en$ironment( condensation may ta=e place in the cell if the sample is drawn into it before the instrument has warmed up properly. %f the mirrors do become fogged( permanently high bac=ground readings can result. #ome mirror materials are more susceptible to humidity. ;or example( sodium chloride windows cloud more easily than those made of sil$er bromide. The mirrors on some instruments can be periodically cleaned. The cell ports in %&s should be co$ered with protecti$e plastic caps when the %& is not in use to pre$ent dust and moisture from contaminating the optics. ;or all uses of an %& instrument( it is important to pre$ent corrosi$e gases and $apors that could damage mirrors( or cell or detector windows( from entering the sample cell. Xeroing %& analy>ers is a critical step. %f the sampler >eros in an atmosphere containing the compound of interest or an interference( and then analy>es air that contains less of the same compound( a negati$e reading or 0error0 message will occur. This reading can occur when the >ero gas filter has become saturated( or if the sampler >eros on humid air and subse1uently analy>es air that is drier than the >ero. ) charcoal canister( sometimes termed a >eroing cartridge or >ero gas filter( must be placed o$er the probe for proper >eroing. 4ote that charcoal has a limited ability to absorb water $apor. These cartridges should be stored in a sealed plastic bag to pre$ent exposure to contaminated atmospheres when not in use. #atu-
.07 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR C, (ppm R ration of the cartridge depends on the nature and concentration of the contaminants that are pulled through it. %f a new cartridge produces an appreciably lower analy>er reading( the old cartridge should be discarded. %f an instrument is >eroed with a contaminated cartridge( a negati$e $alue may occur when ma=ing measurements( the result being low $alues for all measurements because the ambient bac=ground readings may be lower than the concentration in the cartridge used for >eroing. 8hereas some sources recommend using nitrogen for >eroing( others recommend using room air to account for normal humidity conditions./, #ag Sample Collection for $itro s %&ide 'sing an I()* 6*. #et up a portable %& analy>er to the following parameters: 5 4 ,.,F-,.JF 'am( path length R *.5-,* ". )llow the instrument to warm up and e1uilibrated for /5 minutes. 6/. Berform an on-site multipoint calibration at fi$e or more concentrations o$er the range of lAppm to /***ppm. *ote+ Because nitrous oxide supports combustion( the shipments of the compressed gas must comply with ,I C;& /-/-/-- regulations regarding shipment of ha>ardous materials. Calibration for nitrous oxide can fre1uently be done using material a$ailable on-site when sur$eys are done in hospitals( dental offices( and $eterinary operations( because generally the nitrous oxide in use is of sufficient purity. 6+. Xero the instrument while recirculating uncontaminated air through the sample cell. %f the area where the instrument is being calibrated is ser$iced by the same $entilation system as the area to be monitored( it will be necessary to obtain a source of uncontaminated air (or nitrogen or oxygen for >eroing the instrument. ,. %n'ect a =nown $olume of nitrous oxide into the sample cell with a gas-tight syringe through tubing( or by using a septum attached to the sample cell. Calculated the concentration of nitrous oxide in the sample cell: @olume of 4>A in'ected (ul @olume of cell 8hen the instrument reading stabili>es( record meter or display reading. 66. Brepare a calibration graph of ppm (Cs $ersus meter or display reading. 6,. #elect one of the following sampling modes according to the desired form of the data: ambient air or integrated air samples for T8) determinations. 65. "o$e the instrument to the first area to be sampled. ) probe with a sample line can be used to allow more flexibility Thus( the instrument can be placed nearby and the probe can be used to mo$e( for example( around the doors of a sterili>er( or held o$er the shoulder of an employee while opening the door of the sterili>er to get a pea= measurement. 6J. ;or ambient air( turn on the instrument pump and record the readings on the display. %f data are to be expressed as a T8) concentration( an internal datalogging feature or a computer will be needed to store measurements. 6-. Bump air to be analy>ed through the sample cell to purge the cell. Typically( two to three cell $olumes are necessary. 8hen output stabili>es( record the reading as a measurement.
SUMMAR; .0/ 6F. Ese the calibration graph to determine the concentration by mo$ing along the hori>ontal axis to the display reading( and mo$ing to the point on the line that corresponds to this concentration. The ppm $alue for this point on the line can then be read on the $ertical axis. 6I. 3uring each day:s operation( periodically rechec= the calibration by repeating measurements with the calibration gas at three or more points on the graph. ,*. ;or integrated air samples for T8) determinations a clean bag of plastic or other material must first be e$acuated. %t can be done using a personal air sampling pump at the highest airflow a$ailable. ,/. )ttach the plastic bag $ia tubing to a personal sampling pump and pump air from the contaminated area into the bag at a rate calculated to fill the bag o$er the sampling period. This rate will be between +*mD!min and 5**mD!min. Terminate sampling before the bag is F*C full. The pump:s flowrate must be within T5C of the initial setting throughout the sampling period. ,+. )naly>e the bag sample within + hours after completion of the sampling to minimi>e loss of analyte by adsorption and permeation. I(ter&reti(# Meas!re"e(ts with I(frare, A(al%<ers "ost %& instruments express concentration directly in units of parts per million (ppm or percent. .owe$er( some may display results as absorbance or percent transmission. The percent transmission %6T) readout is used with a calibration cur$e to determine the concentration of the sample. The absorbance () scale is related to the 6 T scale by A 4 -log T and is not a linear scale as is the 6 T scale. %t too must be compared to a calibration cur$e in order to determine the actual concentration of the compound being sampled. The calibration cur$es must be prepared in ad$ance using the same control settings (path length( wa$elength( slit width which will be used during measurements and the instrument calibrated immediately prior to sampling to assure the cur$e is still $alid. SUMMAR; This chapter describes direct reading instruments that can identify and measure the concentration of specific compounds in an airborne mixture( which are gas chromatographs (GC ( GC!mass spectrometers (GC!"# ( and infrared (%& instruments including fourier transform %& (;T-%& . There are also many %& de$ices that emit only one wa$elength of %& radiation and this are specific to one airborne compound (e.g.( CA and C*+ ? these are co$ered in detail in this chapter as part of the o$erall discussion of %& instruments. The instruments that can determine the concentrations of specific compounds in an airborne mixture are high-end de$ices that are expensi$e and sophisticated and can be complicated to operate. Generally they ha$e these characteristics in common: )ll are designed to be used with a personal or laptop computer? they are not designed to identify the components of a completely un=nown or 0mystery0 airborne mixture since they must be calibrated with the specific compounds they are measuring? and( because of their si>e and complexity( they are used for area or source sampling rather than routine personal occupational exposure measurements. 8hen selecting between a portable GC or %& instrument for field measurements( two important factors to consider are: %& de$ices re1uire less time to complete an analysis than do GCs. Ten
.01 INSTRUMENTS FOR MULTIPLE SPECIFIC GASES AND VAPORS: GC, GC/MS, AND IR minutes for a CG run is typical( while + minutes or less is typical for an %& instrument reading. GCs ha$e a lower limit of detection for most compounds (in the ppb or ppb range than do %& instruments (in the ppm range . "a'or de$elopments with this category of direct reading instruments has been the increase in functionality due to more powerful microprocessors( and introduction of ad$anced instruments such as the portable GC!"# and ;T-%&. The sampling practitioner should stay current in direct reading technology to ensure that they are aware of the latest ad$ances when selecting instruments for their specific sampling needs. RE$ERENCES ,6. Scentograph &#7S (perating Manual. ;airfleld( 42: #centex #ystems( %nc. ,,. 2oyager &ortable )as Chromatograph Training Manual. 8altham( "): Bhoto$ac( %nc. ,5. /*7 Model )C-899 &roduct nformation. 8alpole( "): Brocess )naly>ers( DDC. ,J. 4ational %nstitute of Accupational #afety and .ealth. * (S/ Manual of Analytical Methods %*MAM:), Method 8;<3, ,th ed.( ". <. Cassinelli and B. ;. A:Connor( eds. 3..# (4%A#. Bublication I,-//6( )ugust( /II,. ,-. /A&S TE= &ortable )C0MS &roduct nformation, n/con,%nc.(<ast #yracuse(4Y. ,F. 1adiation and Chemical /a>ard SimulationH/A&S TE=. Duton( Enited Uingdom: )rgon <lectronics. ,I. Chou( 2. /a>ardous )as Monitors, A &ractical )uide to Selection, (peration and Applications. 4ew Yor=: "cGraw-.ill( +***. 5*. )merican #ociety of .eating( &efrigeration and )ir Conditioning <ngineers( Standard 99<-9??@HMethod of Testing &erformance of #aboratory .ume /oods, )tlanta: )#.&)<( /II5. 5/. M 1A*: Sapph 1e= &ortable Ambient Air Analy>er nstruction Manual ("% J//-*6- . 8altham( "): Thermo <lectron Corporation. 5+.)ASMET= A5-B<9< (perating Manual. )ustin( TW: )ir Luality )nalysis( %nc. 56.)merican #ociety for Testing and "aterials: "ethod 36/J+. Bhiladelphia: )#T". 5,.#ammi( B. #. Calibration of "%&)4 gas analy>ers: <xtent of $apor loss within a closed loop calibration system. A /A C. ,,(l :,*-,5(/IF6. 55.)uide to &ortable nstruments for Assessing Airborne Contaminants at /a>ardous Daste Sites. Gene$a( #wit>erland: 8orld .ealth Argani>ation( /IFF. 5J.De$ine( #. B.( et al. )d$antages and disad$antages in the use of ;ourier transform infrared (;T%& spectrometers for monitoring airborne gases and $apors of industrial hygiene concern. A /A C. ,(- :/F*-/F-( /IFI. 5-.4ational %nstitute of Accupational #afety and .ealth. * (S/ Manual of Analytical Methods %*MAM:), Method EE<<, ,th ed.( ". <. Cassinelli and B. ;. A:Connor( eds. 3..# (4%A#. Bublication I,-//6( )ugust( /II,.
CHAPTER 1&
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING
This chapter co$ers direct-reading de$ices that rely on color change to measure airborne concentration of chemicals. These de$ices fall into three main categories: 3etector tubes and similar products for short-term or grab samples. Tubes (either with a sampling pump or passi$e and badge-li=e units or 0spot plates0 for long-term measurements. <lectronic instruments that collect air samples on a mo$ing tape or in a li1uid and that report the airborne concentration based on the reaction between the target chemical and the reagents in the tape or li1uid. <ach type of colorimetric system represents use of appropriate technology to fill a specific application for the sampling practitioner. 3etector tubes are probably the oldest directreading de$ice still in use and are a con$enient way to rapidly sample for ,**-5** different gases and $apors. 8hen long-term colorimetric de$ices were
introduced( they filled a gap because they allowed longer-duration measurements than the 0grab0 sample with standard detector tubes. )lthough long-term tubes ha$e probably been displaced somewhat by personal-si>e electronic chemical-specific instruments with data-logging features( they are still a good way to sample for some common contaminants and where chemical-specific electronic sensors do not exist. Colorimetric electronic instruments are mainly used in applications where an electrochemical( solid-state( or other direct-reading sensor is not a$ailable. Colorimetric de$ices operate on two broad principles: %n length of stain de$ices the concentration is related to the amount (length of reagent that is discolored( whereas with color intensity de$ices the concentration is related to the degree of color change as compared to a standard. "ost detector tubes are length of stain design( but badges and other products are often based on color intensity readings. ;or $isual reading of results( length of stain
Air Monitoring for Toxic Exposures, Second Edition. By .enry 2. "c3ermott %#B4 *-,-/-,5,65-, 7 +**, 2ohn 8iley 9 #ons( %nc.
*htt&:// www+( )a&,f +' "-
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COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING Figure 1".1. Biston-style pump for detector tubes. (Courtesy of 4extte1( DDC. tronic instruments when immediate results are needed. The primary use for these de$ices is for occupational sampling( since they are not sensiti$e enough to detect the low le$els of contaminants needed for en$ironmental detection. They function on the principle that specific sampling media change color when contaminated air is pulled through them( and they ha$e been a$ailable for J* years or longer. ) typical sampler is a glass tube filled with a solid granular material( such as silica gel( that has been coated with one or more detection reagents that are especially sensiti$e to the target substance and 1uic=ly produce a distinct layer of color change (;igure /6./ . Table /6./ lists some typical reagents used inside the tubes for different gases and $apors. ) calibration scale is printed on the side of the tube( which is used to read concentrations of the measured substances (gases and $apors directly when both ends of the tube are bro=en off and a specified $olume of air is drawn through the tube using a hand-powered pump (typically either of 0piston0 or 0bellows0 design or a battery-powered pump. %n the case where a tube can be used for different concentration ranges( there may be two scales on a tube( each corresponding to a different number of stro=es of the grab sampling pump. %t is important to note that there is a wide $ariety of tubes a$ailable that contain
de$ices are generally considered preferable to color change units since color charts can fade with time or not pro$ide realistic color comparisons( and there is wide $ariation in human perception of color./ Aptical reading instruments are pro$ided with some color intensity detectors as a means of impro$ing accuracy. )ll colorimetric de$ices ha$e temperature( relati$e humidity( and ambient pressure limits as specified by the manufacturer. Aften both a normal range (which is the range o$er which no correction from the manufacturer-pro$ided calibration is needed and a maximum operating range (which denotes the outside limits where calibration correction factors can be applied are specified. )dditionally( some colorimetric de$ices such as tape samplers need some moisture in the air in order to function( and so it is critical to follow the manufacturer:s specification? a relati$e humidity of ,*C is a typical re1uirement for these instruments. Di=e all monitoring processes( colorimetric systems are sub'ect to interferences from nontarget chemicals that can result in either high or low erroneous readings. %n some cases the colorimetric technology has eliminated interferences that pre$ent the use of other monitoring techni1ues( thus ma=ing colorimetric methods the preferred sampling approach. The sampling practitioner must e$aluate possible interferents when selecting the appropriate sampling method for any airborne contaminant. %ETECTOR T'BES 3etector tubes are used for short-term measurements( often termed grab samples. They pro$ide the ability to do direct-reading measurements while in the field for a wide $ariety of gases and $apors. #ince no laboratory analysis is re1uired( they pro$ide fast on-site results and are often considered along with direct-reading elec-
DETECTOR TU3ES .00 T)BD< /6./. Color-Change &eactions in #elected 3osimeter Tubes Gas "easured &eaction Color Change Carbon monoxide YellowHblac=CA T U+Bd(#*6 + HF Bd T C*+ T U+#*6 .+# T .ydrogen sulfide brown 8hiteHdar= Bb(C.6CAA + HF Bb# T +C.6CAA. #*+ T #ulfur dioxide brown GreenH BaCl+ T .+* HF Ba#*6 T +.C/ .C4 T .ydrogen cyanide yellow YellowHred .gCl+ HF .g(C4 + T +.C/ Source+ &oberson( &. 8.( et al. Berformance testing of #ensidyne!Gastec 3osi Tubes for CA( .+#( #*+ and .C4. A /A Conf. &resentation, "ay +/(/IF5.
different chemicals and operate on different reaction principles. The information in this chapter is intended to be a general introduction to this type of air monitoring system. Al,ays refer to the instructions for the specific tube(s being used for accurate operating and safety information. The manufacturer:s instructions for the specific detector tubes are included as an insert in the tube box( and they are critical to proper use of the tubes. #ome manufacturers also publish a more comprehensi$e handboo= or manual for their tube systems. &ead these for information on interferences and relati$e standard de$iations for each tube( as well as the number of stro=es( time between stro=es( and time necessary for color de$elopment( temperature( humidity( and atmospheric pressure effects. The literature also describes the function of each layer in the tube( which is helpful in identifying possible interferences if unanticipated color changes occur. Ather $aluable information is any special precautions such as: whether the tube may emit smo=e or heat up during use? whether the tube re1uires oxygen or airborne water $apor for proper reactions to ta=e place? whether a tube with no reading after a test can be reused for another measurement? if the tube must be held in a certain position (i.e.( $ertically upward for proper operation? and proper disposal procedures for used or out-of-date tubes. There are se$eral different types of tubes depending on the target chemical (;igure
;igure /6.+. 3etector tubes are a$ailable for a wide $ariety of toxic chemicals. (Courtesy of 4extte1( DDC. /6.+ . #imple while others reagents. ;or contains a tubes ha$e 'ust one reagent( ha$e a mixture of se$eral some contaminants the tube prelayer before the color
de$elopment layer to either (a remo$e interfering compounds such as moisture or compounds similar to the target compound or (b otherwise condition the target compound for analysis. ;or example( the prelayer may react with the gas or $apor of interest to con$ert it to a different chemical that can be measured by the detecting
722
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING Figure 1".". Bellows-style pump for detector tubes. (Courtesy of 3raeger #afety( %nc.
reagents. The prelayer in tubes detecting ben>ene is usually designed to remo$e toluene and xylene because these compounds would also react with the detecting layer due to their similarity in structure to ben>ene. Ather gases and $apors are not $ery reacti$e and thus need to be reacted with $ery powerful chemical reagents to brea= down these nonreacti$e compounds into other more readily detectable substances. These powerful reagents may be contained in a separate tube connected in series or in a li1uid-filled ampoule within the main detector tube that is bro=en 'ust before use to coat the granules with a reacti$e reagent. )n example is the 3raeger tube for toluene diisocyanate( which is a long tube with two separate ampoules co$ered with plastic and an indicating layer. %n these situations it is important to follow the specific se1uence indicated in the manufacturer:s instructions and also practice with the tubes before attempting measurements in the field. The portion of the tube containing the ampoule is bent gently until the ampoule brea=s while it is pointing in the right direction so the reagent reaches the correct layer. <ach tube has a specified concentration measuring range that can often be 0expanded0 by $arying the $olume of the sample through ad'usting the number of hand pump stro=es that are drawn. This feature may also allow an ad hoc ad'ustment when the extent of the color change either exceeds or does not reach the calibration scale(s printed on the tube. ;or example( when the length of color change does not reach the calibration scale( additional sampling stro=es can be ta=en (up to a specified maximum until the stain interface extends into the calibration >one. %n this case( the true concentration is determined by di$iding the tube reading by the ratio of the pump stro=es ta=en to the number of stro=es specified in the instructions. #ometimes this information is pre-
sented as 0correction factors0 in the tube:s instruction sheet. 8hen the color change layer exceeds the calibration scale because of higher-than-expected concentration( repeat the test with a fresh tube and sample with half of the standard $olume. %f the color change layer stays within the calibration scale( the tube reading should be doubled to determine the true concentration. There are two different types of pumps a$ailable: the piston $ariety (;igure /6./ and the bellows type (;igure /6.6 . <ach manufacturer has its own design and manufacturing techni1ues. ;or example( some piston-type pumps use orifices to control flow rate while other piston-type pumps use only the resistance of the granules pac=ed in the detector tube to limit flow rate. ) pump with multiple sampling orifices will accurately control both the $olume of air sampled and the rate of airflow during a test. The specific manufacturer:s instructions for each tube will list the re1uired orifice setting and the $olume of air re1uired for each tube( as well as the time re1uired to pull that $olume through the tube. Bellows-type pumps utili>e the tube pac=ing for resistance. "any bellows pump designs ha$e a chain that is taut when the bellows are fully expanded? for these pumps the stro=e is finished when the
DETECTO R TU3ES
#*1 b e ll o w s a r e c o m p l e t e l y o p e n e d a n d t h e c h a i n is ti g h t. E s u a ll y t h e s e p u m p s a r e c a li b r at e d t o p u ll / * * m D o f ai r p e r st r o = e( a n d + / * st r o = e s a r e r e 1 u ir e d . #
tro= e cou nter s are $ery usef ul for bell ows type pum ps( bec ause as note d som e mea sure men ts re1u ire /* or mor e stro =es and it is easy to get distr acte d duri ng this peri od. The stro =e cou nter posi tion mus t be che c=e d with
each stro =e( beca use unle ss the bell ows are full y com pres sed the cou nter may not regi ster the stro =e. #om e pum ps ha$ e ope ning s to brea = off the tube ends ( whi ch is a con $eni ent feat ure. T he pist on pum p han dle may be mar
= e d t o s h o w t h e $ o l u m e t h at t h e p u m p w il l d r a w w h e n t h e h a n d le is l o c = e d i n a c e rt ai
n p o si ti o n. " o st pi st o n p u m p s p ul l / * * m D $ ol u m e o f ai r w it h a f ul l st r o = e( al th o u g h at le a st o n
e has four cali brat ed $olu mes : +5( 5*(5( and /** mD. #om e pist on pum ps also ha$ e stro =e cou nter s that may be aut omati c and cha nge with e$er y stro =e( or they may be cha nge d man uall y by the user. )no ther opti on is the
flo, finis h indi cato r( whi ch is ofte n a butt on that pops up whe n the full $olu me has been sam pled ( thus elim inati ng the need for a stop watc h to time the stro =e. %n addi tion to the basi c han d pum p and dete ctor tube syst em( man ufac ture rs
o ff e r a $ a ri et y o f a c c e s s o ri e s t o e x p a n d t h e u s e f u l n e s s o f d et e ct o r t u b e s. T h e s e
i n cl u d e: B a t t e r y p o w e r e d p u m p s ( ; i g u r e / 6 . , t o u s e i n p l a c e o f t h e h a
n d p u m p s . T h e s e a r e h e l p f u l i n r e d u c i n g f a t i g u e a n d t h e p o t e n
t i a l f o r r e p e t i t i $ e s t r a i n i n ' u r i e s w h e n m a = i n g m u l t i p l e m e a -
s u r e m e n t s ( a n d i n s o m e c a s e s t h e y
f o r t h e t u b e s t h r o u g h
a d d i t i o n a l s t c r a o n = e e s x . t B e y n r d o l t y h > e e m r e s a ( s ; u i r g e u m r e e n / t 6 r . a 5 n g ( e w
h i c h a r e h o t w i r e i n s t r u m e n t s o p e r a t e d b y b a t t e r i e s t h a t a r e
a t t a c h e d t o p u m p s a n d u s e d f o r c e r t a i n g a s e s a n d $ a p o r s s u c h
a s ; r e o n s M a n d o t h e r c h l o r i n a t e d c o m p o u n d s . T h e p u r p o s e o f t h e
Fig ure 1". #. Batt erypow ered pu mp to dra w air thro ugh dete ctor tube s. (Co urte sy of 3ra eger #af ety( %nc.
tanc es that can be mea sure d usin g dete ctor tube s. (Co urte sy of 4ex tte1( DD C p y r o l y > e r i s t o b r e a = d o w n d i f f i c u l t t o -
de tec t co m po un ds int o ot he r co mpo un ds th at ar e m or e ea sil y de tec te d. )
sa m pl e is dr a w n ac ro ss th e he at ed fil a m en t of th e py rol y> er( w hi ch
Fig ure 1".. . Byr oly> er atta chm ent (Byr otec M uses heat to con $ert som e $ap ors into subs
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726
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING T)BD< /6.+. 3raeger #imultaneous Test Uits #imultaneous Compounds Test #et "easured #et %: %norganic )cid gases( e.g.( fumes hydrochloric acid Basic gases( e.g.( ammonia Carbon monoxide .ydrocyanic acid 4itrous gases( e.g.( nitrogen dioxide #et %%: %norganic Carbon dioxide fumes Chlorine .ydrogen sulfide Bhosgene #ulfur dioxide #et %%%: Arganic )lcohols( e.g.( methanol $apors )liphatic hydrocarbons( e.g.( "-hexane )romatics( e.g.( toluene Chlorinated hydrocarbons( e.g.( perchloroethylene Uetones( e.g.( acetone
;igure /6.J. #imultaneous test set permits sampling for multiple substances using special tube sets pro$ided by the manufacturer. (Courtesy of 3raeger #afety( %nc.
decomposes the contaminant( thereby releasing a measurable gas. The decomposition products then pass through the detector tube( causing a change in color relati$e to the concentration. The pyroly>er is also useful for organic nitrogen compounds( one of the products of brea=down being nitrogen dioxide( which is easily monitored. "anifold holders that allow use of se$eral tubes simultaneously (;igure /6.J . ;or example( 3raeger offers
three different sets that are used with a manifold and hand pump for the semi1uantitati$e determination of inorganic gases and organic $apors. <ach test set is able to test for fi$e different gases simultaneously (Table /6.+ in less than one minute and are useful in pro$iding on-site information to firefighters( .a>"at teams( and en$ironmental agencies. )nother special configuration a$ailable from se$eral manufacturers consists of a high-pressure regulator( flow controller( and sampling manifold for testing of compressed breathing air cylinders for conformance with the Compressed Gas )ssociation:s (CG) Grade 3 standard for breathing air. The tubes test for the fi$e substances listed in the standard (carbon monoxide( carbon dioxide( water $apor( oil mist( and oxygen . 4ote that tests for oxygen are especially important when $endors blend breathing air from indi-
DETECTOR TU3ES 72. T)BD< /6.6. "#) %ndustry-#pecific 3etector Tube #ets Type )gricultural set 3etector Tubes Bhosphine (, #ulfur dioxide (+ "ethyl bromide (, .ydrogen cyanide (+ Chlorine dioxide (6 #ulfur dioxide (+ .ydrogen sulfide (6 Chlorine (+ A>one (+ )cetic acid (6 )romatic hydrocarbons (6 Lualitest LD (6 .ydrogen cyanide (6 .ydrogen sulfide (+ Carbon monoxide (+ Lualitest LD (+ Ben>ene (, .exane (+ Carbon monoxide (6 4itrogen dioxide (+ 4itrous fumes (6 4atural gas!methane (, Type #ynthetic Chemicals "anufacturing set 3etector Tubes Toluene (+ Lualitest LD (, <thanol (+ @inyl chloride (+ Trichloroethylene (+ )mmonia (6 Carbon dioxide (6 4itrous fumes (6 .ydrogen sulfide (6 )mmonia (, Chlorine (, .ydrogen chloride (, Carbon monoxide (6 .ydrogen chloride (6 Bhosphine (6 Bhosgene (6 Bhosgene (J Bhosphine (J
Bulp and paper set
Bharmaceutical set
#emiconductor #ets Chemical $apor 3eposition Brocess <tching process <pitaxy process
Betroleum set
"ining set
Crystal growth Brocess *otes+ /. 4umber in parentheses indicates the 1uantity of each tube in the set. +. Lualitest LD detector tubes are used for screening measurements to identify the presence (but not the concentration of many common chemicals including acetone( acetylene( ben>ene( /(6-butadiene( butanes( butylenes( carbon disulfide( carbon monoxide( cyclohexane( diesel oil( ethyl alcohol( ethylene( formic acid( fuel oil( gasoline( hydrogen chloride( hydrogen sulfide( =erosene( li1uefied petroleum gas( methyl ethyl =etone( pentanes and other saturated hydrocarbons( phenol( propane( propyl alcohols( propylene( styrene( perchloroethylene( toluene( town gas (with CA content higher than / $ol. C ( chloroform( $inyl chloride( and xylenes.
$idual gaseous components (oxygen( nitrogen( etc. rather than by compressing ambient air. #pecial 0=its0 or sets of detector tubes selected to represent the type of tubes typically used by different user groups. ;or example( Table /6.6 lists industryspecific sets from "#)? other sets are aimed at .a>"at specialists( en$ironmental specialists( and other distinct users. #ampling probes( sample gas 0coolers0 to cool flue gases and other hot gas samples to ambient temperature for accurate analysis( a warmed holder for
tubes that are carried in cold en$ironments( and other accessories to extend the uses of detector tube de$ices. %n addition to the accessories described abo$e( manufacturers ha$e de$eloped inno$ati$e colorimetric grab sampling approaches based on detector tube technology. ;or example( the 3raeger C"#M chip system uses a chip containing /* measurement capillaries (;igure /6.- for specific gases in an electronic instrument. ) bar code on the chip pro$ides the needed calibration information and other data so the instrument collects the air sample(
727
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING tubes may $ary among tubes and within tubes. ) fine grain si>e is said to pro$ide a uniform distribution of airflow through the tube along with sharp demarcation lines.6 8ithin a gi$en tube( $ariations in particle si>e can lead to striations in the stain and cause a poorly defined (fu>>y stain line. To ensure a high precision indication( gas detector tubes are carefully manufactured to (a ha$e =ey dimensions (such as inner diameter maintained within strict limits( (b control the airflow resistance of the filling reagents and pac=ing material( and (c pro$ide detection reagents with long-term stability. The tubes undergo stringent 1uality control tests: %ndi$idual production lots are tested and calibrated to ensure the highest calibration accuracy for each lot. The certification program described below is an important 1uality control effort for the limited number of tubes co$ered by the program.
Figure 1".%. 3raeger C"#M (chip measurement system uses an optical sensor to detect color change in reagent-filled chips. (Courtesy of 3raeger #afety( %nc. senses the color change( and shows the concentration reading on the instrument:s DC3 display? a data recorder is also a$ailable. Currently( chips are a$ailable for about /different chemicals. =!alit% C (tr l The most important elements of 1uality control in detector tube manufacturing are the purity of the reagents used( grain si>e of the gel or adsorbent( method of pac=ing the tubes( moisture content of the gel( uniformity of the tube diameter( and proper storage precautions to preser$e the shelf life.+ Brecision( accuracy( and reproducibil-ity $ary with the age( conditions of storage( and lot-to-lot manufacturing of these tubes. Grain si>e of the coated granules in the
Dete't r T!$e A''!ra'% The typical accuracy specification for detector tube systems is T+5C when the reading is compared to a =nown gas standard at the occupational exposure concentration. This specification was established by 4%A#. in their certification program conducted between /I-6 and /IF6 and has been continued as an expectation for these de$ices. 8hile other direct-reading instruments may be a$ailable that are more accurate( there are se$eral considerations to =eep in mind when 'udging detector tube accuracy and suitability for use: 3etector tubes re1uire no user calibration o$er their listed shelf life( which is usually two years or more. 3irect-reading electronic instrument generally re1uire regular calibration( often a daily span gas exposure. 3etector tubes are also designed to wor= in a wide array of en$ironmental conditions( from * to ,*KC and at least
DETECTOR TU3ES 72/ /* to I*C relati$e humidity. Correction factors are supplied o$er the specified temperature and relati$e humidity range. Aften a direct-reading electronic instrument has a narrower allowable temperature and humidity range associated with the specified instrument accuracy. )lthough the 4%A#. certification program was discontinued in /IF6( a similar program was implemented in /IFJ by the %nternational #afety <1uipment %nstitute (%#<% and continues today based on )merican 4ational #tandards %nstitute!%nternational #afety <1uipment )ssociation ()4#%!%#<) #tandard /*+., The program includes an e$aluation of both the detector tubes and sampling pump used by each system( and testing is done for pump $olume accuracy and lea=age as well as system accuracy. The tubes are exposed to a specified concentration of test gas( and then a six-person team analy>es each tube:s corresponding length of stain. ;ollowing certification( a manufacturer can use the #<% certification mar= on the product. Ender both the 4%A#. and #<% programs( detector tubes are tested by an independent laboratory and must meet an accuracy le$el of T+5C at test le$els of /( +( and 5 times the )CG%. TD@7 Gthreshold limit !alue) and T65C at half of the TD@7( all at a I5C confidence le$el. The #<% program is limited to tubes in the TD@ range and to about +, listed substances( so by design the certification does not co$er all detector tubes. %n addition to the #afety <1uipment %nstitute (#<% certification program for detector tubes( international bodies ha$e issued standards regulating the properties of detector tubes for measuring airborne contaminants such as the 2apanese %ndustrial #tandard %nstitution (2%# U*F*, ( British #tandard %nstitution (B#56,6 ( 3eutsches %nstitute fur 4ormung or the German #tandard %nstitution (3%466F+ ( and the %nternational Enion of Bure and )pplied Chemistry (%EB)CHBerformance #tandard for 3etector Tubes . Table /6., lists some testing parameters from these standards bodies. %n one study( tests were performed to compare the accuracy of .+#( CA( C*+( and toluene detector tubes from $arious manufacturers. The tests were conducted by the manufacturer sponsoring the study and by three independent laboratories. <ach type of tube was tested using the piston or bellows hand pump from the matching manufacturer. )ll pumps tested passed the specification of G+C lea=age after + minutes with a sealed tube inserted. Gases were filled into a Tedlar bag from a 4%#T-traceable standard cylinder (/*-5* ppm .+#( 5*-,** ppm CA( /** ppm toluene( and *.+-/*C C*+ and a sample $olume drawn according to the manufacturer:s specification. )ll tubes ga$e similar readings within /5C of the standard gas $alues. The results are well within the industry norm of Z+5C accuracy5 Accuracy 2ersus &recision. 8hen reading the manufacturer:s literature for detector tubes( it is important to distinguish between accuracy and precision information. The accuracy of a detector tube system (or any measurement system is the le$el of agreement between the system and a =nown standard( in this case a target gas of =nown concentration. The precision of a measurement $alue is the le$el of agreement between it and other measurement $alues obtained under the same conditions. "any detector tube handboo=s and specification sheets lists a standard de!iation for each tube on the indi$idual data sheet (which often is less than +5C ( but the standard de$iation is a measure of precision. #pecifically( standard de$iation is an indication of how far a group of repetiti$e measurements is expected to stray from the a$erage of all the measurements. This is completely independent of accuracy: ) box
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DETECTOR TU3ES 728 of detector tubes could display a $ery small standard de$iation (i.e.( $ery good precision if all tubes read about the same $alue in a test atmosphere e$en if the $alue was not close to the actual concentration.:/ The concept of standard de!iation can be explained by recalling that two types of errors can occur with de$ices such as detector tubes: &andom errors are slight fluctuations in readings compared to the actual concentrations that occur with tube systems meeting manufacturing speci fications that are used according to directions. The fluctuations are due to $ariations in inner diameters of detector tubes( in densities of filling reagents( in sensiti$ities of reagents( or in the sampling practitioners who read the tubes. To e$aluate random errors( the relati$e standard de$iation is used( which shows in percentage how the reading de$iates from the mean $alue. This $alue is also called the coefficient of !ariation (C@ : &elati$e standard de$iation (C@ (C #tandard de$iation R-------------------------x /** "ean $alue #ystematic errors are due to nonrandom causes such as a lea=ing sampling pump( incorrectly calibrated detector tubes( improper sampling time( inappropriate storage or usage of detector tubes( or presence of interferents. The concept of standard de!iation or C2 does not apply to systematic errors. Interc angeabilit, o" 'ubes and Pumps "rom 0i""erent Manu"acturers. T'ere has been an ongoing contro$ersy for many years about whether it is acceptable to use one manufacturer:s tubes with a hand or other pump from a different $endor. An one hand the pragmatic approach says that once the total sampling $olume and flowrate for a gi$en tube is specified( it is unimportant how that air is drawn through the tube. %n fact many ad hoc sampling arrangements ha$e been de$eloped( such as the multi-tube sampling manifold for ha>ardous waste sites described later in this chapter( that expand the utility of these tubes and their contribution to protecting wor=ers. The opposing $iew applies mainly to the tubes certified as part of the #<% or a similar process: %t states that the tube and pump are tested and certified as part of a 0system(0 and so it is not permissible to substitute unappro$ed e1uipment in the appro$ed system. %n particular( flowrate is an important parameter since it determines the absorption rate for the chemical reactions occurring in the detector tubes to produce the color change and length of stain. The inad$isability of interchanging tubes and pumps was clearly restated in the latest $ersion of )4#%!%#<% #tandard /*+-/II* (&eaffirmed /IIF ,: #ince the indicating beha$ior of a detector tube depends not only on the stro=e $olume( but also on the suction characteristic of the pump( it must be ensured that each detector tube is used only with the prescribed pump. Bump( tube and other components are designed( manufactured( and calibrated together to form a gas detector tube unit. Eser interchange of pumps and tubes or components supplied by different manufacturers may pro$ide erroneous and in$alid measurements of toxic en$ironments. )ccordingly( such interchange is not recommended. Based on this information( a 1ualified professional needs to e$aluate all rele$ant information and determine that any proposed de$iations from certified systems do( in fact( pro$ide ade1uate accuracy and precision before using any ad hoc detector tube monitoring approaches.
729
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING #ometimes manufacturers specify that an interferent will cause a different discoloration of a tube than that specified for the contaminant of interest. ;or example( chlorine causes a bluish stain in one tube( and nitrogen dioxide will turn the same tube a pale yellow color. Therefore( a discoloration significantly different from what is predicted should be considered suspicious. The best pre$ention for erroneous results due to interferences is for the sampling practitioner to e$aluate this potential prior to sampling using the information pro$ided by the tube manufacturer. 'emperature Corrections. Chemical reactions occurring in detector tubes are temperaturedependent. 8ith some detector tubes( reaction rates and physical adsorption of reagents are greatly influenced by tube temperatures. "ost manufacturers specify the normal operating range for their detector tubes as well as a range of temperatures o$er which their tubes will wor=. %f the tube is used at an ambient temperature that is outside of its normal operating range( the reading must be ad'usted using factors stated in their instructions. The tube should not be used at temperatures outside the specified allowable temperature range. Generally( chemical reaction rates are proportional to the temperature( and $arying reaction rates can distort the reading. ;or example( when the temperature is significantly lower than +*KC the reaction will slow down and some 1uantity of the sample may not react in the normal reaction >one but instead will partially react further down the tube. )s a result( a longer layer of pale color change is produced( gi$ing a higher indication. 8hen the temperature is significantly higher than +*KC( the rate of reaction will be higher than normal and the most or all of the sample may react in a shorter distance than the normal reaction >one for +*KC. )s a result( a shorter layer of distinct color change would be produced( gi$ing a
Inter"erences. 3epending on the reaction principles of the tube and the interfering compounds that are present( the interfer-ents may cause higher or lower readings compared to the actual le$el of the target chemical. #ome tubes contain reagents that react directly with the target chemical to produce a color change. %f the air contains substances similar to the target substance that also react with the reagents in the detector tube( the result will be a higher reading. ;or example( many tubes used for chlorine will also react to hydrogen sulfide( ammonia( nitrogen dioxide( ethylene( or halides as well( with the result being an increase in the concentration reading due to these positi$e interf erents. %f any of these compounds are present in the air during sampling( the result will not be specific for chlorine. %n some cases the color change in a tube is due to a p. indicator that responds to the reaction. 8ith this type of tube( any similar acid or basic compound (depending on the tube will react as intereferents( gi$ing a higher indication. )n example of this interference is hydrogen chloride in the air causing a higher reading on some hydrogen cyanide detector tubes. 4egati$e interferences manifest themsel$es as less or no color change when an interferent is present. #ulfur dioxide( for example( when present in an atmosphere being measured for hydrogen sulfide( will produce a lower reading than the concentration actually present. ) second type of detector tube in$ol$es a two-step reaction in which the target substance is oxidi>ed in the pretreatment layer before reacting with the detecting reagent in the analy>er layer. %n this case any non-target compound that also reacts with the oxidi>er (pretreatment reagent may be an interferent if it causes 0consumption0 of the oxidi>er to a degree that oxidation of the target substance is diminished( thus gi$ing a lower indication. )n example of such an interferent is aromatic hydrocarbons to some trichloroethylene detector tubes.
DETECTOR TU3ES
720
T)BD< /6.5. Typical Temperature Correction ;actors for #ol$ent 3etector Tube True Concentration (ppm Tube &eading (ppm /** F* J* ,* +* /* 5 *KC (6+K; /*KC (5*K; +*KC (JFK; 6*KC (FJK; ,*KC (/*,K;
lower also 80 influences 410 indication. 155 Temperature 100 310 125 80 target substance 65 physical adsorption of the to 210 95 60 50 the granules and pac=ing in the tube. )t lower 130 60some of the 40 35 may temperatures( target substance 55 30 20 be physically adsorbed to reagent17 that has 20 13 and thus 10 8 already reacted( it will not react with 6 further along 5 in the tube. 4 )s : 8 :fresh0 reagent a result( a short layer of color change is produced( gi$ing a lower indication. The opposite occurs at higher temperatures: .igher indications may be obtained. Generally the temperature range refers to the tube temperature (not the sample temperature . 8hen air is sampled( its temperature is instantly brought to the temperature of the detector tube. 8hen detector tubes are =ept at a certain ambient temperature for a sufficient period( the tube will reach that temperature. Therefore( the detector tubes 'ust ta=en out of a cool storage location such as a refrigerator ha$e the same temperature as the storage( but it will gradually reach the ambient temperature. Tubes used in hot or cold en$ironments may ha$e to be carried in a temperature-controlled container until used. Calibration is often performed at +*KC (JFK; ( so this is considered as the benchmar= temperature. %f the instruction sheet for the tube indicates that readings are
65affected more than T/*C at other ambient 50temperatures( tube readings should be 40corrected using the factors pro$ided in the 25instructions. Temperature correction factors 15may be a single 0multiplying0 factor for each 7temperature( or presented as a table that 3 con$erts each concentration readings depending on the ambient temperature (Table /6.5 . Correction "or Humidit,. 3etector tubes $ary widely in their reaction to relati$ely humidity (&. . "any are calibrated based on a relati$e humidity of 5*C( and for some there is no effect in the range of * to IIC &. as long as there is no condensing moisture in the tube. )ny re1uired humidity correction factors are gi$en in the detector tube:s instruction sheets. Correction for !tmospheric Press re. The gas concentration (number of molecules present is proportional to the ambient pressure. 3etector tubes are calibrated at normal atmospheric pressure (-J*mm.g ( and usually their readings will not be affected o$er the range of T/*C of normal pressure (approximately JF5-F65 mm .g . %f the pressure at the time of measurement is outside of this range( the tube reading should be corrected as follows:
#1*
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756
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING screen to see if contaminants are present as a preliminary to more complex and accurate methods( or in situations where other methods do not exist or the time factor offered by the direct reading tubes is critical. They are also useful for collecting short-term (pea= or ceiling measurements concurrent with longterm sampling using a sorbent tube or other sample collection de$ice. Their use for compliance sampling is limited to situations where a /5-minute short-term exposure limit (#T<D or a 0ceiling0 standard applies unless a large number of tubes are used to co$er longer exposure periods. Ather uses include area measurements at ha>ardous waste sites and for measurements of lea=s and spills. ) sampling scheme (;igure /6.F has been de$eloped for use as an aid in identifying un=nown chemicals. %t is most useful in situations where indi$iduals are already wearing protecti$e gear( or when a spill or the contents of a drum must be identified 1uic=ly. ;or routine assessments at ha>ardous waste sites( a manifold de$ice to draw air through /* detector tubes at a time has been de$eloped in order to allow for rapid identification of compounds (;igure /6.I . %t can be assembled using two battery-operated( intrinsically safe personal air sampling pumps and a series of +* paired-needle $al$es for sampling and bypass attached to three-way stopcoc=s. This method o$ercomes the lengthy time period re1uired to ma=e /* successi$e measurements on different tubes. ) stopwatch is used to determine when the proper sample $olume has been pulled into each tube? at this point the sampling practitioner switches the flow of contaminated air to the blan= or bypass $al$e by turning the stopcoc=.- .owe$er( considerable setup time is re1uired in order to ensure that each $al$e pro$ides the proper fiowrate and $olume for each indi$idual tube( and the precautions discussed abo$e under 0interchangeability0 apply.
True concentration Tube reading (ppm x -J*(mm .g :: //////////////////////////////////// )tmospheric pressure St ra#e a(, Dis& sal )s detector tubes contain chemicals that are reacti$e( and some reagents might be corrosi$e( care should be ta=en for their storage and disposal. They should be stored in a cool (6+-5*K; ( dar= location. They should ne$er be exposed to direct sunlight( nor should they be stored abo$e normal room temperature. #helf life( represented by the expiration date( is stated on each box of tubes. %t is the period of time within which the calibration accuracy of the tubes can be expected to remain within T+5C. %t is a common practice to refrigerate detector tubes in order to extend their shelf life( but( because the speed of most chemical reactions is sensiti$e to temperature( the tubes must be warmed to ambient conditions prior to use if the tubes are going to perform according to the manufacturer:s specifications. &efrigeration can ensure that the tubes are not exposed to high temperatures( which might decrease the shelf life. Brior to use( detector tubes should be examined $isually for ob$ious problems( such as partial discoloration of an indicating layer. %f tubes change color during storage( some decomposition has probably occurred( and the tubes should be discarded regardless of whether time remains until the expiration date. Esed or date-expired detector tubes should be disposed properly( and in accordance with local ha>ardous waste regulations if appropriate. &efer to the tube:s instructions or "aterial #afety 3ata #heet ("#3# for additional handling and disposal guidance. Use f Dete't r T!$es The primary application for detector tubes are grab sampling measurements as a
DETECTOR TU3ES 75.
Figure 1".). #chematic of simultaneous direct-reading indicator tube system. (&eprinted with permission from Am. nd. /yg. Assoc. C. ,,:J/-( /IF6.
%naccessible locations( such as utility $aults( can be sampled by using a flexible tube attached to the pump and putting the detector tube at the other end. The sample should be drawn directly into the detector tube( meaning that the detector tube should be lowered into the hole attached to the end of the tubing( and not with the tubing in front of the detector tube. The 0tube in front0 configuration a$oids the chance of contaminants adsorbing onto the tubing wall( which will result in a low reading. Dete't r T!$e P!"& Mai(te(a('e a(, Perf r"a('e Che'>s "aintenance is important for detector tube pumps. ;or example( flow orifices may plug from glass fragments from the tube openings( and elastic components such as gas=ets may lose their elasticity from
decomposition products of the detection reaction or unreacted contaminants passing through the tube. Bumps should be accurate to T5C of their stated $olume according to the current performance standards (see Table /6., ., There are two types of performance chec=s that should be conducted on grab sampling pumps to assure accuracy in measurements: lea=age tests and flow rate calibrations. The E.#. A#.) Technical Manual re1uires that each pump used by their compliance officers be lea=-tested before use( as well as calibrated for proper $olume at least 1uarterly or after /** tubes using procedures described in the ManualH !ea1age 'est. A lea=age test should be performed on each pump in order to minimi>e erroneous readings (due to air lea=s around the seals when it is first purchased(
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COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING 5. ;or a bellows pump( insert an unopened tube and compress the bellows completely. Det it sit for 6* minutes and chec= for obser$able expansion. %f there is none( the pump passes. Volume and Fiowrate Cali ration. Calibrate detector tube pumps for proper $olume measurement 1uarterly. Ane of the reasons the pumps lose their $olume capacity is due to the buildup of particles released during the tubes: reactions. These fine particles are pulled into the interior of the pumps and gradually build up. The fiowrate (mD!min determines the reaction rate for many chemical reactions that occur in detector tubes( so refer to the manufacturer:s literature for fiowrate criteria and recommendations for fiowrate tests. #ome pumps ha$e filters( in which case the filter should be chec=ed for buildup which will reduce fiowrate. Proced re J+. Test the detector tube pump for lea=age following the procedures pre$iously described. J6. Connect the inlet of a detector tube pump to the top of a +**-mD bubble burette using Tygon tubing. ;or procedures on the use of bubble burettes see Chapter 5. ;or pumps with limiting orifices to control fiowrate( use a suitable adapter such as a short piece of glass tubing in place of a detector tube (i.e.( do not put a detector tube in line for these pumps . ;or pumps that rely on the resistance of a detector tube to go$ern airflow rate( insert a fresh opened tube in line during measurements. ;or a piston pump continue with steps 6-J and I? for a bellows pump go to step -.
after an extended period of non-use( and periodically during use in accordance with the manufacturer:s instructions. %f a pump has multiple settings( the procedure should be repeated for each setting. &rocedure. #teps /-, refer to a piston pump while step 5 describes the test for a bellows pump. 5F. %f the pump has multiple orifices( turn the rotating head through se$eral re$olutions( finally stopping at the highest fiowrate position. 5I. %nsert an unopened detector tube into the tube holder. Dine up the guide mar=s (usually dots on the pump shaft and housing ( pull bac= the handle all the way( and loc= the piston in the maximum $olume position. J*. 8ait + minutes and release the pump handle slowly in order to pre$ent damage as it springs bac=. 8hen the handle is released( the piston should return completely to the *-mD mar=. %f it does not( the pump is not lea=-tight and the amount of lea=age is indicated by the $olume reading as the handle comes to rest. %f there is greater than 5mD of lea=age in a /**-mD sample $olume within + minutes( or whate$er time is re1uired for the normal pump sampling stro=e( there is excessi$e lea=age which should be repaired to maintain sampling accuracy. J/. %f excessi$e lea=age is found( it usually occurs either at the pump inlet or between the piston and cylinder walls. Dea=age in the cylinder can usually be corrected by cleaning and relubrication. Dea=age at the inlet may result from a poor seal between the detector tube and the rubber inlet tip or between the flange of the rubber inlet tip and the pump body.
DETECTOR TU3ES 75/ J,. %f the pump has flow control orifices( select the orifice to be tested. J5. &e$iew the manufacturer:s literature for the pump being used to determine the number of minutes to wait after pulling the pump handle for the full $olume of the pump to be drawn. JJ. 3ip the bubble burette into bubble solution and pull the pump handle slightly to mo$e the bubble front into the calibrated section of the burette. 4ote the initial position of the soap bubble. Bush the pump handle bac= in( then pull the pump handle all the way out for a full pump stro=e and time the bubble front from the start until it comes to rest. 4ote the final position (reading of the soap bubble. The difference between the initial and final points is the sample $olume. The $olume di$ided by the time is the flowrate. J-. Ese the same procedure to test each orifice for pumps with multiple flow controlling orifices. ;or a bellows-type pump( follow steps through I. JF. #1uee>e the pump( ma=ing sure the bellows are completely and e$enly compressed. )llow the pump to open on its own( measuring the $olume as described in step 5. &epeat two more times and a$erage the three measurements. JI. Compare the results with the manufacturer:s specification for allowable $ariation in total $olume and the time re1uired to draw the total $olume. -*. &epair the pump if the $olume error is greater than T5C and repeat the $olume calibration test. .ield Measurements ,ith Aetector 'ubes. The first step is to identify the target chemical (s ( their approximate concentration(s ( any other compounds (potential interferents that are li=ely to be present during sampling( and rele$ant en$ironmental conditions such as ambient temperature and relati$e humidity. 8ith this information the proper tube can be selected. The tube should also be selected for the concentration range of interest relati$e to the allowable exposure limit? usually this is the )CG%. TD@7 or A#.) permissible exposure limit (B<D . ;rom the tube instruction sheet( note the number of stro=es and the approximate time for the sample to be collected. ;or example( in order to reach a sensiti$ity of / ppm( at least one tube for ben>ene re1uires fi$e stro=es( each + minutes in length? thus a single measurement re1uires /* minutes. %n many cases( the sensiti$ity of a reading can be impro$ed by ta=ing two to four additional stro=es and multiplying the final result by the ratio of the specified number of stro=es to the actual number of pump stro=es. ;or example( if one pump stro=e results in a reading below the first concentration mar= of /* ppm( two more stro=es can be collected. %f the reading is now +* ppm( that $alue can be di$ided by 6 to yield a measurement result of - ppm( which is more specific than reporting a : :G/*ppm0 reading. %t is important to =eep the tube inlet in the proper location during the sampling phase. %f fatigue or aw=ward position ma=es holding the proper position difficult( consider using a Tygon tube between the tube and pump. The tube must remain positioned during the entire sampling period in order to ma=e sure all the air comes from the proper point or source. Proced re for #ello+s P mps /. Brea= off the ends of a fresh detector tube by inserting each end in the tube brea=er hole usually located in the pump head or by using a separate brea=-off de$ice. 3ispose of the bro=en glass in a safe place. 8ith a
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COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING discoloration can 'ust barely be discerned from the original color. %f the end point occurs at an angle( estimate the concentration for each side of the tube and a$erage them. Proced re for Piston P mps -,. "a=e sure the pump handle is all the way in. )lign the index mar=s on the handle and bac= plate of the pump. Brea= off the ends of a fresh detector tube? dispose of the bro=en glass in a safe place. 8ith a two-tube system( connect the ends of the two tubes using the rubber tubing supplied after brea=ing the tube tips. %nsert the tube securely into the pump inlet( ta=ing care that the arrow on the tube points toward the pump. -5. 8ith a multiple orifice pump( select the proper orifice by sliding the loc=ing button on the rotating head forward and turning the head to the designated index number on the flow control plate. 8hen the center line of the loc=ing button is ad'acent to the index mar=( release the button. The springloaded button will then loc= the rotating head in this position. -J. Bull the handle straight bac= (without turning to the sample $olume re1uired (full or partial pump stro=e . The piston will automatically loc= in this position. An some models the handle can be loc=ed on either +5-( 5*-( or /**-mD (full stro=e. )dditionally( some pumps feature a 0onehand0 $al$e (;igure /6./* that allows the sampling to be initiated with only one hand after the piston has been pulled bac=. The time re1uired for the pump to draw its full $olume is important and is specified in the tube:s literature? it is necessary to allow this amount of time in order to collect a full sample. %f the handle is released before sufficient time has
two-tube system( connect the ends of the two tubes using the rubber tubing supplied after brea=ing the tube tips. %nsert the tube securely into the pump inlet( ta=ing care that the arrow on the tube points toward the pump. -/. #1uee>e the bellows pump and release( then wait for the chain straddling the bellows to become taut or for the end of the flow indicator to change color. Bellows-type pumps must be compressed completely flat to get an accurate sample. Both hands may be needed( since e1ual pressure must be applied to both ends of the pump if the entire bellows does not fully compress when only one hand is used. &epeat the compression process as often as specified in the tube:s operating instructions. %f using the stro=e counter( ma=e sure that it registers each stro=e to gi$e an accurate count. -+. 8hen drawing air into a tube( obser$e the tube to note any color change or stain de$elopment. ;or example( if using a hydrogen sulfide tube with a sensiti$ity range of *.5 ppm to /.5 ppm based on /* stro=es( the tube will fully color with a fewer number of stro=es if the concentration is higher than /.5 ppm. 3o not stop until the full number of stro=es has been pulled unless the tube saturates as described abo$e. %f this happens( put in a new tube and pull one-half the specified number of stro=es (in this example 5 stro=es and multiply the reading by a factor of two. -6. &ead the tubes immediately after sampling since some changes in the coloration will occur with time( possibly including a complete fading of the stain. 8here there is a gradation of color change( the end point should be ta=en as that point where the slight
LONG?TERM COLORIMETRIC TU3ES AND 3ADGES 758 window than T+5C of a /*-mm stain . %f se$eral range tubes are a$ailable( choose the tube that will pro$ide a stain length in the upper two-thirds of the tube:s range. <nsure that the concentration inter$al mar=ings on the calibration scale are appropriate for the concentration and setting being e$aluated. ;or example( a sulfur dioxide tube with a /- to 5*-ppm range would not be the best choice for measuring occupational exposures since the permissible exposure limit (B<D is +ppm( while the tube with a 5*-ppm range would probably be mar=ed at 5-ppm inter$als. &egular lea= chec=s of the pump will help to achie$e optimum accuracy by ensuring that the proper air $olume is passing through the tube. ;resh detector tubes will generally be more accurate than tubes beyond their expiration date. 4e$er use detector tubes that are past the posted expiration date. &efrigerated storage will prolong the freshness of the tubes and impro$e accuracy. The recommended storage temperature is 5-/*KC (,/-5*K; . 3etector tubes should not be stored fro>en. ;or optimum accuracy( allow the tubes to warm up to ambient temperature prior to use.
Figure 1".1*. 0Ane-hand0 $al$e permits piston pump sampling with only one hand after the piston is pulled bac=. (Courtesy of 4extte1( DDC.
passed( the $olume will be smaller than is re1uired( with the result being a lower reading than the concentration that is actually present. ,. ;or subse1uent stro=es( if needed( unloc= the pump handle by ma=ing a one-1uarter turn and return it to the starting position. &otate the handle to realign the index mar=s for the next stro=e and pull the handle again. The detector tube should remain in place until all the stro=es ha$e been made. Ma@i"i<i(# the A''!ra'% f Dete't r T!$e Meas!re"e(ts ;ollow these guidelines to maximi>e the accuracy of detector tube readingsJ: 3etector tubes are calibrated at +*KC (JFK; and 5*C relati$e humidity. ;or measurements at significantly different conditions( use the correction factors supplied by the manufacturer. The shorter the stain length( the harder it is for a tube to meet the accuracy specification (e.g.( T+5C of a /-mm-long stain is a much smaller
LONG?TERM COLORIMETRIC TU3ES AND 3ADGES This category of colorimetric de$ices includes long-term detector tubes( direct-reading badges( and 0spot0 plates. Their application is similar to (a sample collection de!ice methods for gases and $apors and (b personal-si>e direct-reading instruments with data-logging capability. )lthough their accuracy is not as high as
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COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING passi$e de$ices where the contaminants enter the tube $ia diffusion. These tubes ha$e the same basic features and characteristics as the short-term detector tubes described abo$e. The main difference $isible to the sampling practitioner is that the calibration scale is not mar=ed in ::ppm0 units? instead it is mar=ed in units of microliters (uD or ppm-hours, and a simple calculation is needed to determine the exposure le$el for comparison to standards expressed in units of ppm. The sample time for most tubes $aries from / hour to , hours( so se$eral tubes may be needed to measure a full F-hour time-weighted a$erage exposure. !ong-'erm 0etector 'ubes "or Pump Sampling. Dong-term tubes for use with a pump usually re1uire $ery low flowrates (in the range of /*-+*mD!min ? not all pumps can achie$e these low rates. The setup is essentially the same as that used for gas and $apor sampling with sorbent tubes discussed in Chapters 5 and J on sample collection de!ice methods. )s with sorbent tubes( the tubes should be =ept in a $ertical position during use. The tubes should also be chec=ed periodically to see if any color change is occurring during the sampling period in order to a$oid the potential of exceeding the tube:s capacity. The information in the tube:s instruction sheet is important since it describes the sampling rate( the total $olume( the sampling time( and the response time for the color change to de$elop as well as temperature( humidity( and pressure correction factors and possible interferents. 8hile the specified sampling time and flowrate must be followed for accurate 1uantitati$e measurements( some flexibility is possible when the tubes are used for screening measurements when it is suspected that the target chemical is present in $ery low concentrations. ;or example( $ery low le$els of sulfur dioxide can cause metal to rust( and these extremely low le$els can
the accuracy of sorbent tubes analy>ed in the laboratory( there are situations where the use of long-term detector tubes can be an ad$antage. %n cases where there is a high degree of employee concern o$er a potential exposure( these tubes gi$e immediate results that are more representati$e of employee exposure (integrated than a series of grab samples using short-term detector tubes. Dong-term tubes for a $ariety of chemicals can be =ept on hand for occasional use( whereas maintaining an in$entory of direct-reading instruments with fresh sensors for infre1uent measurements may not be feasible. Dong-term detector tubes can be $ery useful in situations where a gas or $apor is suspected in that they can be used as a screening de$ice. They can detect much lower le$els than other detector tubes because they can collect samples for a longer period of time. %n a situation where the concern is what compound (rather than how much is present( these tubes can be used for F- to /+- or e$en +,-hour screening samples. %t can be difficult to interpret results when contaminants are present at $ery low le$els due to differences in color changes as compared to the expected color based on a normal sampling time. %t is especially important to remember that these tubes still suffer from the same problem with interferences as the ones used for grab samples. Dong-term or long-duration tubes are a$ailable for a limited number of compounds( but for some of these chemicals the tubes fill a real need in some monitoring situations if the only other a$ailable measurement methods are impingers or expensi$e real-time instruments. L (#?Ter" Dete't r T!$es Dong-term detector tubes fall into two designs: (a those that are used with battery-operated low-flow personal monitoring pumps for acti$e sampling and (b
LONG?TERM COLORIMETRIC TU3ES AND 3ADGES 750 be detected by sampling with a long-term tube for a +,-hour period. Proced re --. Brior to use( test each batch of tubes with a =nown concentration of the air contaminant that is to be measured. &efer to the manufacturer:s data for =ey information and a list of interfering materials. Abser$e the manufacturer:s expiration date( and discard outdated tubes. -F. Brea= off the ends of a tube. Calibrate a pump at the specified flowrate( usually lAmD!min to +* mD! min( with a proper length of tubing and a long-term tube in line using a bubble burette or electronic calibrator. -I. )fter calibration( replace the tube with a fresh one if there was any possibility of contaminants being present( or soap film or water $apor entering the tube during calibration. But the pump on a wor=er or in the area to be sampled. Turn on the pump and record the time or the stro=e number if using a stro=e $olume pump. F*. )t the end of the sampling period( turn off the pump and record the time( and also record the stro=e reading if appropriate. %f the instructions for the tube re1uire that fresh air be pulled through the tube to fully de$elop the color change( ta=e the tube to an area where clean air is present and pull the re1uired amount of air through it. %f only a small amount is re1uired( such as 5**mD( then a suction pump such as a bellows pump can be used? otherwise( the battery-operated pump is used. F/. &ead the tube immediately after the last amount of air is pulled through it. &ead the length of stain in a well-lighted area. &ead the longest length Figure 1".11. Colorimetric diffusion tubes for long-term measurements. (Courtesy of 4extte1( DDC.
of stain if the stain de$elopment is not sharp or is une$en around the tube in order to gi$e a conser$ati$e estimate of exposure. "any tubes will retain their stain for a period of time if the ends are capped. !a""i#e $ete%tor or $o"imeter &u e". Bassi$e detector or dosimeter tubes (;igure /6.// are a$ailable for a $ariety of chemicals. They operate either based on the length-ofstain or the color intensity that de$elops following exposure in the atmosphere to be tested. Their primary ad$antage o$er the acti$e (pump detector tube method is their ease of use in that they are simply opened and hung in place for a period of time. They are designed to be exposed and read after a certain number of hours up to a stated maximum. The basic concept is that increasing exposure times results in longer stain lengths. The stain length is thus related to the product of exposure time and ambient concentration. These de$ices consist of a glass or plastic tube containing an inert granular material or a strip of paper that has been impregnated with a chemical system that reacts with the gas or $apor of interest. )s a result of this reaction( the impregnated chemical changes color. The granular material or paper strip is held in place within the glass tube by a porous plug of a suitable inert material. 3uring use the dosimeter tube is held in a holder that protects the dosime-
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COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING stain length on the Ix axis0 and drawing a line to intersect with the point on a cur$e that corresponds to the number of hours for which monitoring was done( the concentration for the sampling period can be determined. 2Spot Plate2 3adges. #pot plate badges offer another option for passi$e colorimet-ric sampling. "ost are designed for $isual e$aluation and ha$e indicator strips or buttons that change color when a critical accumulation of the target gas is reached. #ome ha$e the colors corresponding to $arious concentrations printed directly on the de$ice or use a colored icon to warn of ha>ardous le$els( while others must be compared to a chart to determine the integrated concentration. The SA.EA 1= system (;igure /6./+ is a self-contained unit that warns of the threshold concentration of a contaminant because the 0exclamation point0 icon becomes $isible. ;or higher resolution and wider measurement range( a slip-in color comparator is a$ailable for selected chemicals. The color comparator contains a color scale that matches the color de$eloped on the badge at different ppb-hr or ppm-hr exposures. Table /6.J shows the chemicals for which the SA.EA 1 badge and color comparator are a$ailable. #ome spot plate de$ices are designed to be used with a sampling pump to increase the minimum detectable le$el and accuracy. %n other respects these units are similar to the passi$e de$ices. )n inno$ati$e colorimetric badge by )ssay Technology relies on an electronic reader to measure ethylene oxide exposures. The ChemChipM personal monitor (;igure /6./6 is worn as a badge on poc=et or lapel. )fter wearing( the test strips encased in the monitor are remo$ed( de$eloped( and inserted into a calibrated reflectance colorimeter. This electronic reader pro$ides on-site readout of chemical exposure in the parts per million (ppm
ter and also helps to minimi>e effects of air currents on performance. The holder has a clip that allows it to be fastened to a collar or poc=et during personal sampling( or to some appropriate ob'ect during area sampling. The dose is deri$ed from length-of-stain dosimeters by reading the length of stain from the calibration cur$e pro$ided with the tubes or printed on the tube. The dose from color intensity units is obtained by comparing the color intensities pro$ided by the manufacturer with the color that de$elops on the dosimeter. 8hen the reading is in units of ppm-hours, this $alue is di$ided by the number of hours in the sampling period to obtain a time-weighted a$erage (T8) exposure result. #ome dosimeters are designed to be used o$er se$eral daysHfor example( units placed in homes to measure formaldehyde. These de$ices often ha$e a calibration for / day:s exposure and for - days: exposure. These dosimeters are usually intended for screening measurements to determine what type( if any( of follow-up measurements should be ta=en. &esults are not considered to be precise. The sampling rate of passi$e colorimet-ric dosimeter tubes is $ery slow( on the order of *./ mD!min. Thus the phenomenon that occurs with some passi$e de$ices in low air mo$ement situations where the air layer ad'acent to the dosimeter becomes depleted of target chemical molecules is not significant for these de$ices. ;or sampling( the dosimeter is either 0bro=en0 open or remo$ed from its protecti$e wrapper( placed $ertically on the person:s lapel or in a gi$en area( and the time is recorded. )t the end of the sample period( the time that the unit is remo$ed is also recorded. The length of stain or the color intensity is compared with the standard or measure pro$ided by the manufacturer( which often is a graph of concentration cur$es corresponding to stain length at a gi$en time. By finding the
COLORIMETRIC ELECTRONIC INSTRUMENTS 765
Figure 1".1". ChemChipM personal monitoring system for determining exposure to ethylene oxide. (Courtesy of )ssay Technology.
COLORIMETRIC ELECTRONIC INSTR'MENTS There are two types of colorimetric electronic instruments: tape-based monitors and wet chemical instruments. Figure 1".12. Colorimetric badges show an immediate color change upon exposure? some de$ices also use a color comparator for more T";e/B"sed Mon!tors accurate determination of concentration. (Courtesy of U9" <n$ironmental( %nc. Baper tape-based instruments use chemically impregnated tape to detect toxic gases. The tape changes color when exposed to the target gas? the color change is detected by a range. The operating range is /*-5**C of the photocell( analy>ed( and translated into a permissible exposure limit( with optimal concentration $alue (;igure /6./, .I These accuracy in the range of 5*-+**C of the B<D. de$ices ha$e the ad$antage of pro$iding %t can reliably measure *./ ppm for an F-hour physical e$idence of the gas concentration shift and lppm o$er a /5-minute #T<D period( from a lea= or release( and typically are less and it meets A#.):s accuracy re1uirements prone to inferences when compared to for compliance measurements. electrochemical and solid-state sensors. ) disad$antage
766
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING TABLE 1".$. Target C'emicals for SAFEA 3; System Colorimetric Passi0e Ba+ges "inimum 3etectable De$el (F .ours *.5*ppm *.*+5 ppm +.+5 ppb /***ppm lppm *.*+6 ppm *.*+6 ppm *.*+5 ppm *.J ppm 6.-5 ppb /.+5 ppb *.*5 ppm /.* ppb +.* ppm #T<D +.F ppm #T<D *.+5 ppm *.*/6 mg!m6 *.**F ppm *./+5 ppm *.**J ppm *.**+ ppm *.J+5 ppb *.*+5 ppm *.J+5 ppb "aximum #ampling Time (.ours ,F ,F /+ /* /* ,F /* ,F ,F /* ,F *.+5 *.+5 ,F ,F ,F /* ,F -+ /+ ,F +, "inimu #amplin Time ("inute /5 5 /5 /5 /5 /5 /5 5 5 /5 5 /5 /5 /5 /5 /* /5 /5 / /5 /5 /5
Chemical )mmonia )niline0 )rsine Carbon dioxide0 Carbon monoxide Chlorine0 Chlorine!Chlorine 3ioxide 3imethyl amine /(/-3imethyl hydra>ine ;ormaldehyde .ydra>ine0 .ydrogen chloride0 .ydrogen fluoride0 .ydrogen sulflde "ercury "ethyl 4itrogen dioxide A>one Bhosgene0 Bhosphine0 #ulfur dioxide +(,-Toluene diisocyanate 0 % n d i c a t e s t h a t a c o
Threshold De$el ,.*ppm-hr *.+ppm-hr /Fppb-hr F*** ppm-hr -ppm-hr *./Fppm-hr Cl+: *./Fppm-hr C/*+: *.+ppm-hr 5ppm-hr ;ront: 6*ppb-hr Bac=: lAppb-hr *.,ppm-hr F.*ppb-hr +.* ppm +.F ppm +ppm-hr ;ront: *./ mg!m6-hr *.*+5 ppm-hr lppm-hr *.*5 ppm-hr *.*/5 ppm-hr 5.*ppb-hr *.+ ppm-hr 5.*ppb-hr
is t h a t b e c a u s e o f c o st a n d c o m p l e x it y( m o st fi x e d i n st a ll a ti o
lor te locations. Thus moisture in the air comparato there can be a in order to r considerable is time function? a relati$e a$ailable delay between a humidity of ,*C for release the and when is a typical chemical. the concentration specification./* Source+ is sensed by the "ore 9 instrument. " These sophisticated tape<n$ironm de$ices are also based monitors ental relati$ely complex use ad$anced ( with mechanical( optics to measure dmen$iron optical( and the light reflected mental.co electronic systems off of the tape m that need before and after pre$enti$e the tape is exposed maintenance and to the sample gas may be prone to stream. %n some n plugging or cases there are s failure( depending multiple u on the ambient measurement s en$ironment. 0windows0Hsome e )dditionally( the ha$e filters to a tapes usually need reduce the c some instrument:s e sensiti$ity and n thus increase the tr measurement a range. #ometimes l two detection a principles are n a l y > e r w it h s a Create PDF files with !t this m"essa#e $% &!r'hasi(# ( )aPDF p &ri(ter *htt&://www+( )a&,f+' "li n g t u b e s r u n t o r e m o
COLORIMETRIC ELECTRONIC INSTRUMENTS 76. offered include phosgene( hydra>ine( ammonia( bromine( chlorine( hydrides (arsine( diborane( disilane( germane( hydrogen selenide( phosphine( silane( and stibine ( hydrogen cyanide( hydrogen sulfide( nitrogen dioxide( o>one( sulfur dioxide( and acid gases (hydrogen bromide( hydrogen chloride( hydrogen fluoride( nitric acid( and sulfuric acid . Tape-based monitors are a$ailable as small passi$e badges( personal monitors( stationary monitors( and sur$ey instruments. )s with all direct-reading instruments( a potential disad$antage that must be in$estigated is the possibility of interference from other airborne chemicals. #ome inter-ferents will cause staining of the tape( while other compounds( such as sulfur dioxide( can bleach the tape( thus causing a lower response. %n addition to e$aluating the possibility of interfering compounds during method selection( it is good practice to routinely inspect the tape following monitoring. %n some cases it may be readily apparent that an interferent was present because the color of the stain will be different than expected. ;or example( whereas T3% commonly stains a tape red-purple( nitrogen dioxide and chlorine will stain the same tape dar= brown. +utoStep Plus4 Portable Paper 'ape 'oxic Gas Monitor. The #cott!Bacharach )utostep BlusM is a paper-based colorimetric portable sur$ey instrument for the measurement of chlorine( formaldehyde( hydra>ine( hydrides( hydrogen chloride( isocyanate compounds( mono methyl-hydra>ine( phosgene( and T3% (;igure /6./5 . %nstrument operation is based on the use of $ariable duration discrete sampling periods. )t the start of a period( the )uto#tep Blus ad$ances to a new piece of tape and chec=s the stray light and tape bac=ground color. %f these are within acceptable limits( the reference light le$el is measured and stored and the sampling pump is started( pulling air through the
Figure 1".1#. 3iagram of a tape-based colorimetric direct reading instrument. (Courtesy of %nternational #ensor Technology.
used in order to monitor o$er a wide range of concentrations:/* Aensity mode for low concentrations( in which the intensity of the stain is compared to calibration data stored in the instrument. 1ate of change mode( which monitors how fast the stain is de$eloping( for measuring higher concentrations. Esing both principles is necessary to co$er a broad concentration range with a high degree of accuracy. 8ith the density mode( there is a flattening of the concentrationresponse cur$e as the concentration increases and the stain approaches its maximum intensity. Beyond this point a higher concentration does not produce much increase in stain intensity. The rate of change mode continually monitors how fast the tape is dar=ening. The higher the concentration the faster the stain de$elops. The instrument can calculate the concentration based on how fast the tape dar=ens. Tape-based monitors are most commonly used for isocyanate compounds because of the difficulty in continuously measuring these compounds. Ather compounds for which tapebased monitors are
767
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING hours when using @)C line $oltage or up to +* hours using the built-in lead acid battery. &elay outputs are also pro$ided for an eternal connection to auxiliary warning de$ices. Cassette life depends upon operational conditions and the resolution of the instrument. %n standard resolution models where gas concentration is low( cassette life can be as great as I** samples (J* hours . )t the other extreme( when operated in conditions where gas concentrations are $ery high( cassette life can be reduced to F hours. Cassette shelf life for unopened cassettes is four months at +*6*KC( and for opened cassettes it is two wee=s. The )uto#tep Blus also functions as a data logger when used with an optional charger!interface unit with software. 8ith this feature all readings are stored in non$olatile memory for future readout and analysis. This capability allows results of sur$eys to be analy>ed and permanently stored. 3ata points are stored in memory at the end of each indi$idual sample period. The duration of these periods range from +* seconds to , minutes( depending on gas concentration. 3ata can be downloaded $ia an &#-+6+ serial port( and the software controls data downloading( analysis( storage( and a wide range of displays and printout options. The instrument:s DC3 panel shows concentration and user-set alarm le$els. %t has audible and $isual alarms( and an acoustic chamber built into the instrument:s handle also pro$ides a tactile warning alarm to the user. The acceptable operating range is 6+-/*,K; temperature and 5-I5C relati$e humidity (noncondensing . Battery ser$ice life of the rechargeable lead acid is /J-+* hours( and it can be operated continuously from line $oltage with the charging unit or interface. The )uto#tep Blus is ED appro$ed as intrinsically safe for Class %( 3i$ision % operation. %t weighs ,.-5 pounds.
Figure 1".1.. )utostep BlusM tape-based instrument has tape cassettes for different toxic gases and $apors. (Courtesy of #cott %nstruments.
tape. 3uring the sample period the instrument continuously measures the light reflected off of the tape and compares the reading to a preset threshold. %f a high concentration of contaminant is present( the reflected light le$el will e$entually exceed the threshold. 8hen this happens( the sampling period is ended at , minutes and the stain intensity is used to determine the concentration. The accuracy is whiche$er is greater between either Z/5C of reading or lppb!A.Alppm (depending on the scale .// Two modes of operation allow the )uto#tep Blus to effecti$ely operate as both a portable lea= sourcing instrument and a temporary continuous area monitor: The 0demand sampling mode0 pro$ides an indication of toxic gas le$els in as little as /5 seconds and is typically used when determining the presence or source of lea=s. The user controls the sampling time and the initiation of new samples. The 0continuous sampling mode0 is useful in area monitoring applications where a fixed monitor is not installed or is una$ailable. The de$ice can monitor continuously for up to J*
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SUMMAR; 76/ Bet Che"i'al C l ri"etri' Te'h(i:!es ) uni1ue niche in air monitoring techni1ues is filled by wet chemical colorimetric instruments. These de$ices collect an air sample in a manner that remo$es the target compound from the air stream and transfers it to a li1uid chemical reagent where it undergoes a color change that is proportional to its concentration. These instruments are selected when there is not a more feasible or con$enient direct reading techni1ue for the application. The most common reasons for using wet chemical instruments are the need to monitor $ery low le$els of acutely toxic compounds( or the presence of interfering compounds that render other techni1ues unsatisfactory. ;or example( one manufacturer ma=es a wet chemical analy>er that is capable of continuously monitoring for compounds such as ammonia( chlorine( formaldehyde( hydra>ine( hydrogen chloride( hydrogen cyanide( hydrogen fluoride( hydrogen peroxide( mercaptans( nitrogen dioxide( 4Ax( phenol( phosgene( sulfur dioxide( titanium oxides( nicotine( and total aldehydes. The target compound can be changed by changing reagent(s and( in some cases( by changing the analytical module tray which contains the necessary glassware. The unit is extremely sensiti$e and for many of the analyses can operate o$er a range of maximum sensiti$ity of *- to *.+5-ppm full scale( detecting as minute a 1uantity as *.**5 ppm or 5ppb of the gas to be measured( ad'ustable to a full scale range of more than /*ppm. )s an illustration( to measure formaldehyde with this instrument( an air sample is continuously drawn into the unit and any formaldehyde that is present is scrubbed with a sodium tetra-chloromercurate solution that contains a fixed 1uantity of sodium sulfite. )cid-bleached pararosaniline is added( and the intensity of the resultant color is measured at 55*-nm wa$elength by a colorimeter and is displayed on a digital readout and stored in memory. Esing the standard range( concentrations of *-+ ppm can be measured? a low-le$el option will measure *-5** ppb. The minimum detection le$el is *.**5 ppm (5 ppb using the *- to *.5-ppm full-scale setting or / C of other scales. There is a lag time of se$eral minutes between collection of the sample and when the results are a$ailable( although I*C of the $alue is displayed within less than 5 minutes. The instrument is usable at temperatures of ,*-/+*K;( with an optimum range of J*-F*K; and 5-I5C &.. SUMMAR; Colorimetric direct-reading de$ices rely on color change to measure airborne concentration of chemicals and include: detector tubes and similar products for short-term or grab samples? tubes (either with a sampling pump or passi$e and badge-li=e units or 0spot plates0 for long-term measurements? and electronic instruments that collect air samples on a mo$ing tape or in a li1uid and that report the airborne concentration based on the reaction between the target chemical and the reagents in the tape or li1uid. Colorimetric de$ices operate on two broad principles: %n length of stain de$ices the concentration is related to the amount (length of reagent that is discolored( whereas with color intensity de$ices the concentration is related to the degree of color change as compared to a standard. Di=e all monitoring processes( colorimetric systems are sub'ect to interferences from nontarget chemicals that can result in either high or low erroneous readings. %n some case the colorimetric technology has eliminated interferences that pre$ent the use of other monitoring techni1ues. )ll colorimetric de$ices ha$e temperature( relati$e humidity( and ambient pressure limits as specified by the manufacturer. #ome col-
761
COLORIMETRIC S;STEMS FOR GAS AND VAPOR SAMPLING tor TubesHShort Term Type for Toxic )ases and 2apors in Dor'ing En!ironments. )4#%: 4ew Yor=( /IIF. FJ. Technical 4ote (T4 -/,6( )ccuracy Comparisons of &)< #ystems Gas 3etection Tubes. &)< #ystems( #unny$ale( C)( /III. F-. &oberson( &. Tech CornerHCommon -uestions 1e!ol!ing Around Aetector Tube Accuracy. Clearwater( ;D: #ensidyne( +**6. FF. Uing( ". @.( B. ". <ller( and &. 2. Costello. ) 1ualitati$e sampling de$ice for use at ha>ardous waste sites. A /A C. ,,(F :J/5-J/F( /IF6. FI. Accupational #afety and .ealth )dministration. (S/A Technical Manual. 8ashington( 3.C: E.#. 3epartment of Dabor( +**6 (http:!!www.oshaslc.go$!dts!osta!otm! otm[extended[toc.html . I*. Chou( 2. /a>ardous )as Monitors, A &ractical )uide to Selection, (peration and Applications. 4ew Yor=: "cGraw-.ill( +***. I/. Dhat Jou Should Kno, About )as Aetection. <xton( B): #cott!Bacharach Gas 3etection Broducts( +**6 (http:!!www.scottbacharach.com . I+. Scott0Lacharach AutoStep &lus= &roduct nformation, <xton( B): #cott!Bacharach( +**6 (http:!!www.scottbacharach.com .
orimetric de$ices such as tape samplers need some moisture in the air in order to function. The sampling practitioner must e$aluate possible interferents and whether the operating conditions are suitable when determining if colorimetric systems are a good option for their sampling needs.
RE$ERENCES F+. Cohen( B. #.( and C. #. "cCammon( 2r.( eds. Air Sampling nstruments for E!aluation of Atmospheric Contaminants, Ith ed. Cincinnati( A.: )CG%.( +***. F6. Blog( B. ).( and B. 2. Luinlan( eds. .undamentals of ndustrial /ygiene, 5th ed. %tasca( %D: 4ational #afety Council( +**+. F,. #amer( #. &( and 4. 8. .enry. The use of detector tubes ;ollowing )#T" "ethod ;--6I-F5 for "easuring Bermeation &esistance of Clothing. A /A C. 5*(J :+IF-6*+( /IFI. F5. )merican 4ational #tandards %nstitute! %nternational #afety <1uipment )ssociation #tandard /*+-/II* (&eaffirmedlIIF . American *ational Standard for )as Aetec-

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CHAPTER 12

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