xvEPA
          United States      Atmospheric Research and
          Environmental' Protection  Exposure Assessment Laboratory
          Agency        Research Triangle Park NC 27711
                        EPA/600/4-89/01 7
                        June 1988
          Research and Development
Compendium of
Methods for the
Determination of Toxic
Organic Compounds in
Ambient Air

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                                            EPA/600/4-89/017
                                                June 1988
Compendium of Methods for the
 Determination of Toxic Organic
    Compounds in Ambient Air
                       by

          William T. Winberry, Jr. and Norma T. Murphy
                  Engineering-Science
               One Harrison Park, Suite 200
               401 Harrison Oaks Boulevard
                    Gary, NC 27513

                       and

                     R. M. Riggan
               Battelle-Columbus Laboratories
                    505 King Avenue
                  Columbus, OH 43201
                      Revisions

  Original Compendium     EPA/600/4-84/041     April 1984
  First Supplement        EPA/600/4-87/006     September 1986
  Se ondSup^ment      EPA/600/4-89/018     June 1988
    Atmospheric Research and Exposure Assessment Laboratory
            Office of Research and Development
            U S. Environmental Protection Agency
             Research Triangle Park, NC 2771 1
            Begion 5 , Lilrrar:
            230 S. Dearborn-
            Chicago, IL   &C

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                               Disclaimer




7h^±±±?  ^l?^^  h«  be?" ^** Wholly or  in
                                ii

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                                    CONTENTS
                                         /                                Page
 INTRODUCTION	     v

 TABLE 1.  Brief Method Description and Applicability  	    vi

 TABLE 2.  Method Applicability to Compounds of Primary Interest  ....  viii

 METHODS:

 T01   Determination of Volatile Organic Compounds in  Ambient Air
      Using Tenax® Adsorption and Gas Chromatograph (GC/HS)  	 T01-1
 T02   Determination of Volatile Organic Compounds in  Ambient Air
      by Carbon Molecular Sieve Adsorption and Gas Chromatography/
      Mass Spectrometry (GC/MS)  	 T02-1
 T03   Determination of Volatile Organic Compounds in  Ambient Air
      Using Cryogenic Preconcentration Techniques and Gas Chromatog-
      raphy with Flame lonization and Electron Capture Detection .... T03-1
 T04   Determination of Organochlorine Pesticides and
      Polychlorinated Biphenyls in Ambient Air 	 T04-1
 T05   Determination  of Aldehydes and Ketones in Ambient
      Air Using High Performance Liquid Chromatography (HPLC).  	 T05-1
 APPENDIX A - EPA Method 608
 T06   Determination of Phosgene in Ambient Air Using
      High Performance Liquid Chromatography (HPLC)	T06-1
 T07   Determination of N-Nitrosodimethylamine in Ambient
      Air Using Gas Chromatography	T07-1
 T08   Determination of Phenol and Methyl phenols (Cresols)
      in Ambient Air Using High Performance Liquid
      Chromatography (HPLC)	T08-1
 T09   Determination of Polychlorinated Dibenzo-p-Dioxins
      (PCDDs) in Ambient Air Using High-Resolution Gas
      Chromatography/High-Resolution Mass Spectrometry 	 T09-1
 T010  Determination of Organochlorine Pesticides in  Ambient
      Air Using Low Volume Polyurethane Foam (PUF) Sampling
      with Gas Chromatography/Electron Capture Detector (GC/ECD)  .  . . .T010-1
T011  Determination of formaldehyde in Ambient Air Using
      Adsorbent Cartridge Followed By High Performance
      Liquid Chromatography (HPLC)  	  . . .T011-1
T012  Determination of Non-methane Organic Compounds (NMOC)
      in Ambient Air Using Cryogenic Preconcentration
      and Direct Flame lonization Detection (PDFID).	T012-1
T013  Determination of Polynuclear Aromatic Hydrocarbons
      (PAHs) in Ambient Air Using High Volume Sampling
      with Gas Chromatography/Mass Spectrometry (GC/MS)
      and High Resolution Liquid  Chromatography Analysis	T013-1
T014  Determination of Volatile Organic Compounds (VOCs)  in
      Ambient Air Using SUMMA® Polished Canister Sampling
      and Gas Chromatographic (GC)  Analysis	T014-1
                                         iii

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                                    FOREWORD

     Measurement and monitoring  research efforts  are  designed  to  anticipate
potential environmental  problems, to  support  regulatory actions by  developing
an in-depth understanding  of  the nature  and  processes  that impact  health  and
the ecology, to  provide  innovative  means of  monitoring compliance  with  regu-
lations, and to  evaluate the  effectiveness  of  health  and environmental  pro-
tection efforts through the monitoring  of long-term  trends.  The  Environmental
Monitoring Systems  Laboratory,  Research  Triangle Park,   North  Carolina,  has
responsibility for:   assessment   of  environmental  monitoring  technology  and
systems; implementation  of  Agency-wide  quality assurance  programs  for  air
pollution measurement systems; and  supplying  technical  support to  other  groups
in the Agency,  including  the  Office of Air and  Radiation, the  Office  of Toxic
Substances, and the Office of Enforcement.

     Determination of toxic organic compounds in ambient air is  a  complex task,
primarily because  of the  wide  variety of compounds  of interest  and the lack of
standardized sampling  and analysis  procedures.  This  methods  Compendium  has
been prepared to provide  a  standardized format for  such analytical procedures.
A core set of five methods is presented in the original  document.   In an effort
to update  the  original  Compendium,  four specific methods  have  been developed
and published  in a supplemental  document.   In addition to the  Compendium and
Supplement, five  new  methods  have  been prepared  for  inclusion.  With  this
addition, the  Compendium  now  contains fourteen standardized sampling and anal-
ysis procedures.   As advancements are made, the  current methods may  be modified
from time to time  along with new additions to the Compendium.
                                  Gary J. Foley
                                     Director
                   Environmental Monitoring Systems Laboratory
                  Research Triangle Park, North Carolina,  27711
                                        iv

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            UB XSo osa                                     jaded





                             INTRODUCTION



    This  Compendium has been  prepared  to P^^^^eVestfd^par^es,  w,u,

environmental regulatory agencies,  « weu           .  organic compounds in

specific guidance  on the **ER? ««  '/l.'ulS^e-nt (T'AD) was —'•"
XM.M. ^^^^
"zed format,  for selected toxic organic compounds.
    Tne current  Compendium  consists

ered to be of ^ primary  l-POrt"«« '» ^Tompend iu™ fS time to time, as  such

Additional methods will be Pj»«»  '" "e ™K" were selected to cover as  many
methods become available.  The original methods were se       selected).   The
                                   analte «™
                                          we
 methods  become  available.  The  origina  metos we           selected).   The

 compounds as possible  (i.e., ™J"Ple analyte  «™           „   oups of

                                           '      be determined by tbe
 more general methods.

     Each of the methods writeups is self *»Jt.1».M l-Juding pertinent liter-

 ature citations) and can be  used .1"deefetllhd.entAm°rfictat'ne society  for  Besting and
                                                may be  required  in  the


 future.
      „„„ ...

 SSSasH
  of the specific task.
  ealuate the applicability of the method before use.
   (1) Riggin, R. M.,  "Technical  Assistance  Document


      °f  •OXnmentaiaprStectT5r Agency",  Xswroh TH angle" Park,  North  Carolina,


      1983.

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               PUB
                                                                JSdBd P8|OAO9J
             TABLE 1.  BRIEF METHOD DESCRIPTION AND APPLICABILITY
Method
Number
   Description
          Types of
    Compounds Determined
TO-1
TO-2
TO-3



TO-4



TO-5



TO-6


TO-7

TO-8




TO-9
Tenax GC Adsorption
and GC/MS Analysis
Carbon Molecular Sieve
Adsorption and GC/MS
Analysis
Cryogenic Trapping
and GC/FID or ECD
Analysis

High Volume PUF
Sampling and GC/ECD
Analysis

Dinitrophenylhydrazine
Liquid Impinger Sampling
and HPLC/UV Analysis

High Performance Liquid
Chromatography (HPLC)

Thermosorb/N Adsorption

Sodium Hydroxide Liquid
 Impinger with High Per-
formance Liquid Chromato-
graphy

High Volume Polyurethane
Foam Sampling with
High Resolution Gas
Chromatography/High
Resolution Mass Spec-
trometry (HRGC/HRMS)
Volatile, nonpolar organics
(e.g., aromatic hydrocarbons,
chlorinated hydrocarbons)
having boiling points in the
range of 80° to 200°C.

Highly volatile, nonpolar
organics (e.g., vinyl chloride,
vinylidene chloride, benzene,
toluene) having boiling points
in the range of -15° to +120°C.

Volatile, nonpolar organics
having boiling points in the
range of -10° to +200°C.

Organochlorine pesticides and
PCBs
Aldehydes and Ketones



Phosgene


N-Nitrosodimethylami ne

Cresol/Phenol




Dioxin
                                      vi

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            pu» .
       TABLE 1.  BRIEF METHOD DESCRIPTION AND APPLICABILITY (Continued)
Method
Number
   Description
        Types of
  Compounds Determined
TO-10
TO-11
TO-12
TO-13
TO-14
Low Volume Polyurethane
Foam (PUF) Sampling With
Gas Chromatography/Electron
Capture Detector (GC/ECD)

Adsorbent Cartridge Followed
By High Performance Liquid
Chromatography (HPLC)
Detection

Cryogenic Preconcentration
and Direct Flame lonization
Detection (PDFID)

PUF/XAD-2 Adsorption
with Gas Chromatography
(GC) and High Performance
Liquid Chromatography
(HPLC) Detection

SUMMA® Passivated Canister
Sampling with Gas Chromatog-
raphy
Pesticides
Formaldehyde
Non-Methane Organic
Compounds (NMOC)
Polynuclear Aromatic
Hydrocarbons (PAHs)
Semi-Volatile and
Volatile Organic
Compounds (SVOC/VOCs)
                                     vii

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     1II3UIUIUIAU3 pUB .43O5O.W
       TABLE 2.  METHOD APPLICABILITY TO COMPOUNDS OF PRIMARY INTEREST
   Compound
   Applicable
    Method(s)
         Comments
Acenaphthene
Acenaphthylene
Acetaldehyde
Acetone
Acrolein
Acrylonitrile

Aldrin
Allyl Chloride

Aroclor 1242, 1254
 and 1260
Benzaldehyde
Benzene

Benzyl Chloride
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(e)pyrene
Benzo(g,h,i)perylene
Benzo(k)fl uoranthene
Butyraldehyde
Captan
Carbon Tetrachloride

Chlordane
Chlorobenzene
Chloroform

Chloroprene
 (2-Chloro-l,3-buta-
 diene)
Chlorothalonil
Chlorpyrifos
Chrysene
Cresol
Crotonaldehyde
4,4'-DDE
4,4'-DDT
1,2-Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1»2-Dichloroethylene
TO-14
TO-14
TO-5, TO-11
TO-11
TO-5, TO-11
TO-2, TO-3

TO-10
TO-2, TO-3

TO-10

TO-5
TO-1, TO-2, TO-3,
TO-14
TO-1, TO-3, TO-14
TO-13
TO-13
TO-13
TO-13
TO-13
TO-13
TO-11
TO-10
TO-1, TO-2, TO-3
TO-14
TO-10
TO-1, TO-3, TO-14
TO-1, TO-2. TO-3
TO-14
TO-1, TO-3
 TO-10
 TO-10
 TO-13
 TO-8
.TO-11
 TO-4
 TO-4
 TO-14
 TO-14
 TO-14
 TO-1,  TO-3,  TO-14
 TO-14
 TO-14
Extension of TO-11
Extension of TO-11
Extension of TO-11
TO-3 yields better recovery
data than TO-2.

TO-3 yields better recovery
data than TO-2.
TO-14 yields better recovery
data.
Extension of TO-11

Breakthrough volume is very
low using TO-1.
Breakthrough volume is very
low using TO-1
The applicability of these
methods for chloroprene has
not been documented.
 Extension of TO-11
                                      vili

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 TABLE 2.   METHOD APPLICABILITY TO COMPOUNDS OF PRIMARY INTEREST (Continued)
                             Applicable
                              Method(s)
Compound
         Comments
1,2-Dichloropropane
1,3-Dichloropropane
Dichlorovos
Dicofol
Dieldrin
2,5-Dimethylbenzaldehyde
Dioxin
Endrin
Endrin Aldehyde
Ethyl Benzene
Ethyl Chloride
Ethylene Dichloride
 (1,2-Dichloroethane)
4-Ethyltoluene
Fluoranthene
Fluorene
Folpet
Formaldehyde
Freon 11
Freon 12
Freon 113
Freon 114
Heptachlor
Heptachlor  Epoxide
Hexachlorobenzene
 and a-Hexachloro-
 cyclohexane
Hexachlorobutadiene
Hexachlorocyclopenta-
 diene
Hexanaldehyde
Indeno(l,2,3-cd)pyrene
Isovaleraldehyde
Lindane  (a-BHC)
Methoxychlor
Methyl Benzene
Methyl Chloride
Methyl Chloroform
 (1,1,1-Trichloroethane)
Methylene  chloride
Mexacarbate
Mirex    '
Naphthalene
Nitrobenzene
N-Nitrosodimethylamine
trans-Nonachlor
                       TO-14
                       TO-14
                       TO-10
                       TO-10
                       TO-10
                       TO-11
                       TO-9
                       TO-10
                       TO-10
                       TO-14
                       TO-14
                       TO-1, TO-2, TO-3
                       TO-14
                       TO-14
                       TO-13
                       TO-13
                       TO-10
                       TO-5, TO-11
                       TO-14
                       TO-14
                       TO-14
                       TO-14
                       TO-10
                       TO-10
                       TO-10

                       TO-10
                       TO-14

                       TO-10
                       TO-11
                       TO-13
                       TO-11
                       TO-10
                       TO-10
                       TO-14
                       TO-14
                       TO-1, TO-2, TO-3
                       TO-14
                       TO-2, TO-3, TO-14
                       TO-10
                       TO-10
                       TO-13
                       TO-1, TO-3
                       TO-7
                       TO-10
Extension of TO-11
Breakthrough volume very low
using TO-1.
Extension of TO-11

Extension of TO-11
Breakthrough volume  very  low
using TO-1.
                                       1x

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  TABLE 2.  METHOD APPLICABILITY TO COMPOUNDS OF PRIMARY INTEREST (Continued)
    Compound
 Non-methane Organic
  Compounds
 Oxychlordane
 Pentachlorobenzene
 Pentachlorphenol
 p.p1-  DDE
 P,p'-  DDT

 Perchloroethylene
  (tetrachloroethylene)
 Phenanthrene
 Phenol
 Phosgene
 Polychlorlnated bi-
  phenyls  (PCBs)
 Propanal
 Propionaldehyde
 Pyrene
 Ronnel
 1,2,3,4-Tetrachloro-
  benzene
 1,1,2,2-Tetrachloro-
  ethane
 o-Tolualdehyde
 m-Tolualdehyde
 p-Tolualdehyde
 Toluene

 1 »2,3-Trichlorobenzene

 1,2,4-Trichlorobenzene
 1,1,2-Trichloroethane
 Trichloroethylene

 2,4,5-Trichlorophenol
 1,2,4-Trimethylbenzene
 1,3,5-Trimethylbenzene
 Valeraldehyde
 Vinyl Benzene
 Vinyl Chloride
 Vinyl Trichloride
Vinylidine Chloride
 (1,1-dichloroethene)
o.m.p-Xylene
Applicable
 Method(s)
                                                         Comments
 TO-12

 TO-10
 TO-10
 TO-10
 TO-10
 TO-10

 TO-1, (TO-2?),  TO-3,

 TO-13
 TO-8
 TO-6
 TO-4, TO-9

 TO-5
 TO-11
 TO-13
 TO-10
 TO-10

 TO-14

 TO-11
 TO-11
 TO-11
 TO-1,  TO-2, TO-3,
 TO-14
 TO-10, TO-14

 TO-14
 TO-14
 TO-1, TO-2, TO-3,
 TO-14
 TO-10
 TO-14
TO-14
TO-11
TO-14
TO-2, TO-3, TO-14
TO-14
TO-2, TO-3, TO-14

TO-1, TO-3, TO-14
                   TO-2 performance has not been
                   documented for this compound.
                   Extension of TO-11
                   Using  PUF in  combination with
                   Tenax* GC solid  adsorbent.
                   Extension  of  TO-11
                   Extension  of  TO-11
                   Extension  of  TO-11
                  Using PUF  in combination  with
                  Tenax* GC  solid adsorbent.
                  Extension of TO-11

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                              TOl              Revision 1.0
                              T01              April, 1984
1.    Scope
     , ,  The document describes a generalized protocol for Election
         and determination of certain volatile organic compounds
         which can be captured on Tenax* GC (poly(2,6-0lphenyi
         -;:::;;;::> srrrs r--
     , t  r;::^;: -iir anil-!—- r
          to acco-odate procedures currently in use.  Hoover, such
     within each laboratory

1.3
           Organ1cs having boiling points 1. tne range of WP""-^
           80» - 200-C.  However, not all compounds falling int. th,s
           category can be determined. Table 1 gives a  listing of
              Ids for .Men the method has been used.  "^ compo.d
           may yield satisfactory results but validate by the ,nd,»,du.l
           user is required.
  2.    Applicable Documents

       2.1  ASTM Standards:
            D1356    Definitions of Terms Related to Atmospheric Sampling
                   and Analysis.
            E355    Recommended Practice for Gas Chromatography Terms and
                   Relationships.

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                                 T01-2
        2.3   Other documents:

              Existing procedures  (1-3).
              U.S.  EPA Technical Assistance  Document  (4).

 3.     Summary of  Protocol

        3.1   Ambient  air is drawn through a cartridge containing M-2
             grams of Tenax and certain volatile organic compounds are
             trapped  on the resin while highly volatile organic compounds
             and most  inorganic atmospheric constituents pass through the
             cartridge.  The cartridge is then transferred to the
             laboratory and analyzed.
       3.2   For analysis the cartridge is placed in  a heated chamber and
             purged with an inert  gas.  The inert gas transfers the
             volatile organic compounds from the  cartridge onto a cold trap
             and  subsequently onto  the front of the GC column which is held
             at  low temperature (e.g.  - 70'C).  The GC column temperature is
             then  increased (temperature  programmed)  and the  components
             eluting  from the  column are identified and quantified by mass
             spectrometry.   Component  identification  is normally  accomplished,
             using  a  library search routine, on the basis of  the  GC retention
             time and  mass  spectral characteristics.   Less sophistacated
             detectors (e.g. electron  capture or flame ionization) may be
             used for  certain applications but their suitability for a given
             application must be verified by the user.
      3.3    Due to the complexity of ambient air samples only high resolution
             (i.e. capillary) GC techniques are considered to be acceptable
             in this protocol.

4.     Significance

      4.1    Volatile organic compounds are emitted into the  atmosphere from
            a variety of sources including industrial  and  commercial
            facilities, hazardous waste storage facilities, etc.   Many of
            these  compounds are toxic; hence knowledge of  the levels of

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                                 TO!-3
           such materials in the ambient atmosphere is required in order
           to determine human health impacts.
     4.2   Conventional air monitoring methods (e.g. for workspace
           monitoring) have relied on carbon adsorption approaches with
           subsequent solvent desorption.  Such techniques allow
           subsequent injection of only a small portion, typically 1-5%
           of  the sample onto the GC system.  However, typical
           ambient air concentrations of these compounds require a more
           sensitive  approach.  The thermal  desorption process, wherein
           the entire sample  is introduced  into the analytical  (GC/MS)   ,
           system  fulfills  this need  for enhanced  sensitivity.

5.     Definitions

      Definitions used in this document and  any user prepared SOPs should
      be consistent with ASTM 01356(6).   All abbreviations and symbols
      are defined with this document at the  point of use.

6.    INTERFERENCES

      6.1   Only compounds  having a similar mass spectrum and GC retention
            time compared to  the compound of interest will interfere  in
            the method.  The  most commonly  encountered interferences  are
            structural  isomers.
      6.2   Contamination of  the Tenax  cartridge with the compound(s)
            of interest  is  a  commonly encountered  problem in  the method.
            The user  must  be  extremely  careful  in  the preparation, storage,
             and handling of the  cartridges  throughout the entire  sampling
             and analysis process  to minimize this  problem.

  7.    Apparatus

        7 i    Gas Chromatograph/Mass Spectrometry system - should be capable
               of subambient temperature programming.  Unit mass resolution
               or better  up  to 800 amu.  Capable of  scanning 30-440 amu region
               every 0.5-1 second.  Equipped  with data system  for instrument
               control  as well as data acquisition,  processing and storage.

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                              TO!-4
  7.2    Thermal  Desorption  Unit  -  Designed  to accommodate Tenax
        cartridges  in  use.   See  Figure 2a or b.
  7.3    Sampling System - Capable  of accurately and precisely
        drawing  an  air flow  of 10-500 ml/minute through the Tenax
        cartridge.   (See Figure  3a or b.)
  7.4    Vacuum oven  - connected  to water aspirator vacuum supply.
  7.5    Stopwatch
  7.6    Pyrex disks - for drying Tenax.
  7.7    Glass jar - Capped with Teflon-lined screw cap.   For
        storage of purified  Tenax.
 7.8   Powder funnel - for  delivery of  Tenax  into cartridges.
 7.9   Culture tubes - to hold individual  glass  Tenax cartridges.
 7.10   Friction top can  (paint can)  - to hold clean Tenax cartridges.
 7.11   Filter holder - stainless steel or aluminum (to  accommodate
       1 inch diameter filter).   Other sizes may  be used if desired.
       (optional)
 7.12   Thermometer  - to record ambient temperature.
 7.13   Barometer (optional).
 7.14   Dilution  bottle -  Two-liter with  septum cap for  standards
       preparation.
 7.15   Teflon  stirbar  - 1 inch long.
 7.16   Gas-tight glass syringes  with stainless steel  needles -
       10-500  M!  for standard injection onto GC/MS system..

 7.17   Liquid microliter syringes - 5,50 uL for injecting neat
       liquid standards into dilution bottle.
 7.18   Oven - 60  +  5°C for equilibrating dilution flasks.
 7.19   Magnetic  stirrer.
 7.20   Heating mantel.
 7.21   Variac
 7.22   Soxhlet extraction  apparatus and  glass  thimbles - for purifying
      Tenax.
7.23   Infrared lamp - for drying Tenax.
7.24  GC column - SE-30 or  alternative  coating,  glass capillary or
      fused silica.

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                                  T01-5
      7.25  Psychrometer -  to determine ambient  relative  humidity.
            (optional).

8.    Reagents and Materials

      8.1   Empty Tenax cartridges - glass or stainless steel (See
            Figure la or b).
      8.2   Tenax 60/80 mesh  (2,6-diphenylphenylene oxide polymer).
      8.3   Glasswool - silanized.
      8.4   Acetone - Pesticide quality or equivalent.
      8.5   Methanol -  Pesticide  quality, or equivalent.
      8.6   Pentane - Pesticide quality or equivalent.
      8.7   Helium - Ultra pure,  compressed  gas.  (99.9999%)
      8.8  Nitrogen -  Ultra pure,  compressed gas.  (99.9999%)
      8.9   Liquid nitrogen.
       8 10  Polyester  gloves - for handling  glass Tenax  cartridges.
       8.1.1  Glass Fiber Filter -  one inch diameter, to fit in filter holder.
             (optional)
       8.12  Perfluorotributyl amine (FC-43).
       s'.13  Chemical Standards - Neat compounds of interest.  Highest
             purity available.
       8.14  Granular activated charcoal - for  preventing contamination of
             Tenax cartridges during storage.

  9.     Cartridge Construction and Preparation

        9.1   Cartridge  Design
              9.1.1   Several cartridge designs  have been reported in the
                      literature (1-3).  The  most common  (1)  is shown in
                      Figure la.  This design minimizes contact of the
                      sample with metal surfaces, which can lead to
                      decomposition in certain cases.  However, a
                      disadvantage of this design is the need to rigorously
                      avoid  contamination of the outside portion of the
                      cartridge since  the entire surface is  subjected to the
                      purge  gas stream during the desorption porcess.

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                             TO!-6
               Clean polyester gloves must be worn at all times
               when handling such cartridges and exposure of the
               open cartridge to ambient air must be minimized.
       9.1.2   A second common type of design (3) is shown in
               Figure Ib.   While this design uses a  metal  (stainless
               steel) construction, it eliminates the need to avoid
               direct contact with  the exterior  surface  since only
               the  interior of the  cartridge is  purged.
       9.1.3    The  thermal  desorption  module and  sampling  system
               must  be  selected  to  be  compatible  with  the  particular
               cartridge design  chosen.  Typical  module designs
               are shown in  Figures 2a and b.  These designs are
               suitable for  the cartridge designs shown in Figures
               la and Ib, respectively.

9.2   Tenax Purification
      9.2.1   Prior to use the Tenax resin is subjected  to a
              series of solvent extraction and thermal treatment
              steps.  The  operation should be conducted  in an area
              where levels of volatile organic compounds  (other than
              the extraction solvents  used)  are  minimized.
      9.2.2   All glassware used in Tenax  purification as  well  as
              cartridge materials should be  thoroughly cleaned by
              water  rinsing followed by an acetone rinse and  dried
              in  an  oven at  250°C.
      9.2.3    Bulk Tenax is  placed  in  a glass extraction thimble
              and held  in place with a plug of clean glasswool.
              The resin is then placed in the soxhlet extraction
             apparatus and extracted sequentially with methanol
             and then pentane for 16-24 hours (each solvent) at
             approximately 6 cycles/hour.   Glasswool for cartidge
             preparation should be  cleaned in the same manner as
             Tenax.
     9.2.4   The extracted Tenax is immediately placed in an open
             glass  dish and heated  under an  infrared lamp for two

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                           T01-7
             hours in a hood.   Care must be exercised to avoid
             over heating of the Tenax by the infrared lamp.
             The Tenax is then placed in a vacuum oven (evacuated
             using a water aspirator) without heating for one hour.
             An inert gas (helium or nitrogen) purge of 2-3
             ml/minute is used to aid in the removal of solvent
             vapors.  The oven temperature is then increased to
             110°C, maintaining inert gas flow and held for one
             hour.  The oven temperature control is then shut
             off  and  the oven is allowed to cool to room temperature.
             Prior  to opening the oven, the oven is slightly
             pressurized with nitrogen  to  prevent contamination
             with ambient air.  The  Tenax  is  removed  from  the oven
             and  sieved  through a  40/60 mesh  sieve  (acetone  rinsed
             and  oven dried)  into  a  clean  glass  vessel.   If  the  Tenax
             is not to be used  immediately for  cartridge  preparation
             it should be stored  in  a clean glass  jar having a
             Teflon-lined screw cap  and placed  in  a desiccator.

9.3   Cartridge Preparation  and  Pretreatment
      9.3.1  All  cartridge  materials are  pre-cleaned as described
              in Section 9.2.2.   If the glass cartridge des< ]n shown
              in Figure la is employed all  handling should bd
              conducted wearing polyester gloves.
      9.3.2   The cartridge  is packed by placing a 0.5-lcm glass-
              wool plug in the base of the cartridge and then
              filling the cartridge to within approximately 1 cm
              of the  top.  A 0.5-lcm glasswool plug is placed in
              the top of the cartridge.
      9.3.3   The cartridges are then thermally conditioned by
              heating for four hours at 270°C under an inert gas
              (helium) purge (100 -  200 ml/min).

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                                   T01-8
             9.3.4   After the four hour heating period the cartridges
                     are allowed to cool.  Cartridges of the type shown
                     in Figure la are immediately placed (without cooling)
                     in clean culture tubes having Teflon-lined screw caps
                     with a glasswool cushion at both the top and the bottom.
                     Each tube should be shaken to ensure that the cartridge
                     is held firmly in place.   Cartridges of the type shown
                     in Figure Ib are allowed to cool  to room temperature  under
                     inert gas purge  and are  then closed with stainless  steel
                     plugs.
            9.3.5    The  cartridges are  labeled and placed in a  tightly
                     sealed metal can  (e.g. paint can or similar friction
                     top  container). For cartridges of the type  shown
                     in Figure la the culture tube, not the cartridge,is
                     labeled.
            9.3.6   Cartridges should be used for sampling within 2 weeks
                    after preparation and analyzed within two weeks after
                    sampling.  If possible the cartridges should be stored
                    at -20°C in a clean freezer (i.e.  no solvent extracts
                    or other sources  of volatile organics contained in the
                    freezer).

10.    Sampling
      10.1   Flow rate and Total  Volume Selection
            10.1.1   Each  compound has a characteristic  retention volume
                    (liters  of air  per gram of  adsorbent)  which  must  not
                    be  exceeded.  Since the retention volume  is  a  function
                    of  temperature, and possibly  other  sampling  variables,
                    one must  include  an  adequate  margin  of safety  to
                    ensure good collection  efficiency.   Some  considerations
                    and guidance  in this  regard are provided  in  a  recent
                    report (5).  Approximate breakthrough volumes  at  38°C
                    (100°F) in liters/gram  of Tenax are provided in Table 1.
                    These retention volume  data are supplied only  as  rough
                    guidance and are subject to considerable variability,
                   depending on cartridge design as well as sampling
                   parameters and atmospheric conditions.

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                      T01-9
10.1.2  To calculate the maximum total  volume of air which
        can be sampled use the following equation:
                 VMAX
where
        VMAX  1s the calculated maximum total volume in liters.
        Vb    is the breakthrough volume for the least retained
              compound  of  interest  (Table 1) in liters per gram
              of Tenax.
        W    is the weight  of  Tenax  in the  cartridge, in grams.

         1.5 is a  dimensionless safety factor  to allow for
         variability in atmospheric conditions.  This factor
         is appropriate for temperatures  in  the  range of
         25-30°C.   If higher temperatures are  encountered  the
         factor should be increased (i.e. maximum  total  volume
         decreased).
 10.1.3  To calculate maximum flow rate use the following
         equation:
                          -  MX x 1000
                     XHHA    t
  where

          QMAX   1s the  calculated maximum  flow  rate  in milli-
                 leters  per minute.
          t      is the  desired sampling time in minutes.   Times
                 greater than  24 hours (1440 minutes) generally
                 are unsuitable because the flow rate required
                 is too low to be accurately maintained.
  10.1.4  The maximum flow rate QMAX should yield a linear flow
          velocity of 50-500 cm/minute.  Calculate the linear
          velocity corresponding to the maximum flow rate
          using  the  following  equation:
                         irr

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                               T01-10
        where

                B  is the calculated linear flow velocity in
                   centimeters per minute.
                r  is the internal radius of the cartridge in
                   centimeters.
                If B is greater than 500 centimeters per minute
                either the total  sample volume (VMAX) should be
                reduced or the sample flow rate (QMAX) should be
                reduced by increasing the collection time.   If B is
                less  than  50 centimeters per minute  the  sampling rate
                (QMAX)  should be  increased by  reducing the sampling
                time.   The  total  sample  value  (VMAX)  cannot  be
                increased due to  component breakthrough.
        10.1.4   The flow rate calculated  as  described  above  defines
                the maximum  flow  rate allowed.   In general,  one  should
                collect  additional samples  in parallel, for  the  same
                time period  but at lower  flow rates.   This practice
                yields a measure of quality control and is further
                discussed in  the literature (5).  In general, flow
                rates 2 to 4  fold lower than the maximum flow rate
                should be employed for the parallel samples.   In
               all cases a constant flow rate should be achieved
               for each cartridge since accurate integration of the
               analyte concentration requires  that the flow  be
               constant over the  sampling period.

10.2  Sample Collection

      10.2.1  Collection of an accurately known volume of air
              is critical  to the accuracy of the results.  For
              this reason the use of mass flow controllers,
              rather than conventional  needle valves or orifices
              is highly recommended, especially at low flow
              velocities (e.g. less  than 100 mi 11 niters/minute).
              Figure  3a illustrates  a sampling system utilizing
              mass flow controllers.   This system  readily allows
              for  collection of parallel  samples.   Figures 3b
              shows a  commercially available system based on
              needle  valve  flow controllers.

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                     TOl.-ll
10 2 2  Prior to sample collection insure that the sampling
        flow rate has been calibrated over a range including
        the rate to be used for sampling, with a "dummy"
        Tenax cartridge in place.  Generally calibration
        is accomplished using a  soap bubble flow meter
        or calibrated  wet test meter.  The  flow calibration
        device  is  connected  to the  flow  exit,  assuming
        the  entire flow system is sealed.   ASTM Method
        D3686 describes an  appropriate calibration scheme,
         not requiring a sealed  flow system downstream
         of the pump.
 10 2 3  The flow rate should be checked  before and after
         each sample collection.   If the sampling interval
         exceeds four  hours the  flow rate should be checked
         at  an  intermediate point during sampling as well.
         In  general, a rotameter should  be  included, as    .
         showed in Figure 3b, to allow observation of the
         sampling  flow rate  without disrupting the  sampling
         process.
  10 2 4 To collect an air sample the cartridges  are  removed
          from the sealed container just  prior to  Initiation
          of the collection process.  If  glass cartridges
          (Figure la)  are employed they must be handled
          only  with polyester gloves and should not contact
          any other  surfaces.
  10.2.5   A  particulate filter and  holder are  placed on
          the inlet  to the cartridges  and the  exit end
          of the cartridge is connected  to  the sampling
          apparatus.   In many sampling situations  the use
          of a  filter  is  not necessary if  only the  total
          concentration of  a component is  desired.  Glass
           cartridges of the  type shown in  Figure  la are
           connected using teflon ferrules  and Swagelok
           (stainless steel  or  teflon) fittings.   Start  the
           pump and record the  following  parameters on an
           appropriate data sheet (Figure 4):  data, sampling
           location, time, ambient temperature, barometric

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                      T01-12
         pressure,  relative  humidity, dry gas meter reading
         (if  applicable)  flow  rate, rotameter reading (if
         applicable),  cartridge number and dry gas meter
         serial  number.
 10.2.6   Allow the  sampler to  operate for the desired time,
         periodically  recording the variables listed above.
         Check flow rate  at  the midpoint of the sampling
         interval if longer  than four hours.
         At the  end of the sampling period record the
         parameters listed in  10.2.5 and check the flow
         rate and record  the value.  If the flows at the
         beginning  and end of  the sampling period differ
         by more than 10% the  cartridge should be marked
         as suspect.
 10.2.7   Remove  the cartridges (one at a time) and place
         in the  original container (use gloves for glass
         cartridges).   Seal the cartridges or culture tubes
         in the  friction-top can containing a layer of
         charcoal and package for immediate shipment to
         the laboratory for analysis.   Store cartridges
         at reduced temperature (e.g.  - 20°C) before analysis
         if possible to maximize storage stability.
 10.2.8   Calculate and record the average sample  rate for
        each cartridge according to the following equation:

               A =        _
where

        QA  = Average flow rate in ml/minute.
        Ql,  Q2,	QN = Flow rates determined at
        beginning,  end, and immediate  points
        during sampling.

        N   = Number  of points averaged.
10.2.9  Calculate  and  record the  total  volumetric flow for
        each  cartridge using the  following  equation:

                 V  =   T x QA
                        1000

-------
                                T01-13
           where

                   Vm = Total volume sampled in liters at measured
                        temperature and pressure.
                   T£ = Stop time.
                   T] = Start time.
                   T  - Sampling time = T£ - T-J , minutes
           10.2.10 The total volume (Vs) at standard conditions,
                   25°C and  760 mmHg, is calculated from the
                   following equation:
            where
                                   PA    298
                       Vs = Vm x —750 x  273 + tA
                    PA =  Average  barometric  pressure, mmHg
                    t/\ =  Average  ambient  temperature, °C.
11.    GC/MS Analysis

      11.1  Instrument Set-up
            11.1.1  Considerable variation from one laboratory to
                    another is expected in terms of instrument configuration.
                    Therefore each laboratory must be responsible
                    for verifying that their particular system yields
                    satisfactory results.  Section 14 discusses specific
                    performance criteria which should be met.
            11.1.2  A block diagram of the typical GC/MS system
                    required for analysis of Tenax cartridges is
                    depicted in Figure 5.  The operation of such
                    devices is described in 11.2.4.  The thermal
                    desorption module must be designed  to accommodate
                    the particular cartridge configuration.  Exposure
                    of the  sample to metal surfaces  should be
                    minimized and only stainless  steel, or nickel metal
                    surfaces should be employed.

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                       T01-14
         The volume of tubing and fittings leading from
         the cartridge to the GC column must be minimized
         and all  areas must be well-swept by helium carrier
         gas.
 11.1.3  The GC column inlet  should  be  capable  of  being
         cooled to  -70°C  and  subsequently increased  rapidly
         to  approximately 30°C.   This can  be most  readily
         accomplished  using a  GC  equipped  with  subambient
         cooling  capability (liquid  nitrogen) although
         other approaches  such as manually cooling the
         inlet of the  column  in liquid  nitrogen may  be
         acceptable.
 11.1.4   The specific  GC column and  temperature program
         employed will be  dependent  on  the specific compounds
         of  interest.  Appropriate conditions are described
         in the literature (1-3).  In general a nonpolar
         stationary phase  (e.g. SE-30, OV-1) temperature
         programmed from 30°C to 200°C at 8°/minute will
         be suitable.  Fused silica bonded phase columns
         are preferable to glass columns since they are
        more rugged and  can  be inserted directly into
         the MS ion source, thereby eliminating the need
        for a  GC/MS transfer  line.
11.1.5  Capillary column  dimensions  of  0.3 mm ID and 50
        meters long are generally appropriate although
        shorter  lengths may be sufficient in many cases.
11.1.6  Prior  to  instrument calibration or sample  analysis
        the  GC/MS system  is assembled as shown  in  Figure
        5.   Helium purge  flows (through the  cartridge)
        and  carrier flow  are  set  at  approximately  10 ml/
        minute and  1-2 ml/minute  respectively.   If applicable,
        the  injector sweep flow  is set  at 2-4 ml/minute.

-------
                          T01-15
     11.1.7  Once the column and  other system components  are
             assembled and the various flows established  the
             column temperature is increased to 250°C for
             approximately four hours (or overnight if desired)
             to condition the column.
     11.1.8  The MS and data system are set according to  the
             manufacturer's instructions.  Electron impact
             ionization (70eV) and an electron multiplier gain
             of  approximately 5 x 10* should be employed.
             Once  the entire GC/MS system has  been setup the
             system  is calibrated as  described in  Section 11.2.
             The user should  prepare  a detailed standard
             operating procedure  (SOP) describing  this process
             for the particular  instrument  being used.

11.2  Instrument Calibration

      11.2.1  Tuning and  mass standarization of the MS system
              is performed according to manufacturer's instructions
              and  relevant information from the user prepared
              SOP.  Perfluorotributyl amine should generally
              be employed for this purpose.  The material
              is  introduced directly  into the  ion  source
              through a molecular leak.  The instrumental
              parameters  (e.g. lens  voltages,  resolution,
              etc.)  should  be  adjusted to give the relative
               ion abundances  shown  in Table 2  as well  as
               acceptable  resolution  and  peak shape.   If
               these approximate  relative abundances  cannot
               be achieved,  the ion  source may require cleaning
               according  to manufacturer's instructions.
               In  the event that the user's instrument cannot
               achieve these relative ion abundances, but
               is  otherwise operating properly, the user
               may adopt another set of relative abundances
               as  performance criteria.

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                    T01-16
         However,  these alternate  values  must  be  repeatable
         on a  day-to-day basis.
 11.2.2  After the mass standarization  and  tuning process
         has been  completed  and  the appropriate values
         entered into  the  data system the user should
         then  calibrate the  entire system by introducing
         known  quantities  of the standard components
         of interest into  the system.   Three alternate
         procedures may be employed for the calibration
         process including 1) direct syringe injection
         of dilute vapor phase standards, prepared
         in  a dilution  bottle, onto the GC column, 2)
         Injection of dilute vapor phase standards
         into a carrier gas  stream directed through the
         Tenax cartridge, and 3)  introduction of permeation
        or diffusion tube standards  onto a Tenax cartridge.
        The standards preparation procedures for each
        of these approaches are  described in Section
        13.  The following paragraphs  describe the
        instrument calibration process  for each  of
        these  approaches.
11.2.3  If the instrument is to  be calibrated  by  direct
        injection  of a gaseous standard,  a  standard
        is prepared in a dilution  bottle  as described
        in Section 13.1.   The GC column is  cooled
        to -70°C (or,  alternately, a portion of the
        column  inlet  is manually cooled with liquid
        nitrogen).  The MS and data system  is  set
        up for  acquisition as described in  the relevant
        user SOP.  The  ionization filament should be turned
       off  during the  initial 2-3 minutes of the run to
       allow oxygen and other highly volatile components
       to elute.  An appropriate volume (less than 1 ml)
       of the gaseous  standard is injected onto the GC
       system using an accurately calibrated gas tight syringe,

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                     TO!-17

        The system clock is started and the column is
        maintained at -70°C (or liquid nitrogen inlet cooling)
        for 2 minutes.   The column temperature is rapidly
        increased to the desired initial temperature (e.g.  30°C).
        The temperature program is started at a consistent
        time (e.g. four minutes) after injection.  Simultaneously
        the ionization  filament is  turned  on  and  data acquisition
        is initiated.  After the last component of interest has
        eluted acquisiton  is terminated and the data is processed
        as described in Section 11.2.5.  The  standard injection
        process  is repeated using different standard volumes as
        desired.
11.2.4   If the  system  is  to be calibrated  by  analysis of
         spiked  Tenax cartridges a  set of  cartridges  is
         prepared as  described  in  Sections  13.2 or 13.3.
         Prior to analysis the  cartridges  are  stored  as
         described in Section  9.3.  If glass cartridges (Figure  la)
         are employed care must be taken to avoid direct
         contact, as described earlier.  The GC column is
         cooled to -70°C, the collection loop is immersed in
         liquid nitrogen and the desorption module is
         maintained at 250°C.   The inlet valve is placed in the
         desorb mode and the standard cartridge is placed in
         the desorption module, making certain that no leakage
         of purge gas  occurs.   The  cartridge  is  purged
         for  10  minutes and then the  inlet valve  is placed  in
         the  inject  mode  and the liquid nitrogen  source removed
         from the collection trap.   The GC column  is maintained
         at  -70°C for  two minutes  and subsequent  steps are  as
         described  in  11.2.3.  After the process  is complete the
          cartridge  is  removed  from the desorption module and
          stored for  subsequent use as described in Section  9.3.

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                            T01-18
      11.2.5   Data processing for instrument calibration involves
               determining retention times, and integrated characteristic
               ion intensities for each of the compounds of interest.
               In addition, for at least one chromatographic run,the
               individual mass spectra should be inspected and
               compared to reference spectra to ensure proper
               instrumental  performance.   Since the steps involved
               in data processing are highly instrument specific, the
               user should prepare a SOP  describing the process  for
               individual use.   Overall performance criteria for
               instrument calibration are provided  in  Section 14.   If
               these criteria  are not achieved  the  user should refine
               the instrumental  parameters and/or operating
               procedures to meet these criteria.

11.3  Sample Analysis

      11.3.1   The sample analysis process is  identical  to that
               described in  Section 11.2.4 for  the  analysis of standard
               Tenax cartridges.
      11.3.2   Data  processing for sample data  generally involves
               1) qualitatively  determining the  presence or absence
               of each component  of interest on  the basis of a set
               of characteristic  ions and  the retention  time  using
               a  reverse-search  software  routine, 2) quantification
               of each identified  component by  integrating the intensity
               of a  characteristic ion and comparing the value to
               that  of the calibration standard,  and 3)  tentative
               identification of  other components observed using a
               forward  (library) search software routine.  As for
               other user specific processes,  a  SOP should be prepared
               describing the specific operations for  each individual
               laboratory.

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                               T01-19
12.    Calculations

      12.1  Calibration Response Factors

            12.1.1  Data from calibration standards is used  to  calculate
                    a response factor for each component of  interest.
                    Ideally the process involves analysis of at least
                    three calibration levels of each component  during  a
                    given day and determination of the response
                    factor (area/nanogram injected) from the linear
                    least squares fit of a plot of nanograms injected   ,
                    versus area (for the characteristic ion).
                    In general quantities of component greater
                    than 1000 nanograms should not be injected
                    because of column overloading and/or MS response
                    nonlinearity.
            12.1.2  In practice the daily routine may not always
                    allow analysis of three such calibration standards.
                    In this situation calibration data from consecutive
                    days may  be pooled  to yield a response factor,
                    provided  that analysis of  replicate  standards
                    of the  same concentration  are shown  to agree
                    within 20% on the consecutive days.  One standard
                     concentration,  near the midpoint  of  the  analytical
                     range of  interest,  should  be chosen  for  injection
                    every day to determine  day-to-day response
                     reproducibility.
             12.1.3  If substantial  nonlinearity is  present  in
                     the  calibration  curve a nonlinear least  squares
                     fit (e.g. quadratic)  should be  employed.
                     This process  involves fitting  the data  to
                     the following  equation:
                           Y = A +  BX + CX2
             where
                     Y = peak area
                     X = quantity of component, nanograms
                     A,B, and C are coefficients in the equation

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                                T01-20
      12.2  Analyte Concentrations
            12.2.1
           where
           12.2.2
           12.2.3
           where
Analyte quantities on a sample cartridge are calculated
from the following equation:

     YA = A + BXA  +
YA  is the area of the analyte characteristic ion for
    the sample cartridge.
XA  is the calculated quantity of analyte on the sample
    cartridge, in nanograms.
A,B, and C are the coefficients calculated from the
calibration curve described in Section  12.1.3.
If instrumental response is essentially linear  over  the
concentration range of interest a linear equation
(C=0 in the equation above) can be employed.
Concentration of analyte in the original  air sample  is
calculated from the following equation:

             CA=^
                    CA  is the calculated  concentration of  analyte  in
                        nanograms per liter.
                    V^  and  XA are  as  previously defined in Section
                    10.2.10 and 12.2.1, respectively.
13.    Standard Preparation
      13.1   Direct Injection
            13.1.1  This  process  involves preparation of a dilution
                    bottle  containing the desired concentrations
                    of compounds  of  interest for direct injection
                    onto  the  GC/MS system.

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                         TO!-21
13.1.2  Fifteen three-millimeter diameter glass beads
        and a one-inch Teflon stirbar are placed in a
        clean two-liter glass septum capped bottle and
        the exact volume is determined by weighing the
        bottle before and after filling with deionized water.
        The bottle is then rinsed with acetone and dried at 200°C.
13.1.3  The amount of each standard to be injected into the
        vessel is calculated from the desired injection quantity
        and volume using the following equation:

                         WT  . WLX  VB
                              Vl
     where
              WT is the total quantity of analyte to be injected
                 into the bottle in milligrams
              MI is the desired weight of analyte to be injected
                 onto the GC/MS system or spiked cartridge in
                 nanograms
              Vj is the desired GC/MS or cartridge injection
                 volume (should not exceed 500) in microliters.
              VB is total volume of dilution bottle determined
                 in 13.1.1,  in  liters.
        13.1.4 The  volume of  the neat standard  to be  injected
                 into the dilution  bottle  is determined using
                 the  following  equation:
                               W
where
               Vj is the total  volume of neat liquid  to  be  injected
                  in microliters.
                d is the density of the neat standard in grams  per
                  milliliter.

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                          T01-22
 13.1.6  The bottle is placed in a 60°C oven for at
         least 30 minutes prior to removal of a vapor
         phase standard.
 13.1.7  To withdraw a standard for GC/MS injection
         the bottle is removed from the oven and stirred
         for 10-15 seconds.   A suitable gas-tight microber
         syring warmed to 60°C,  is inserted through
         the septum cap and  pumped three times  slowly.
         The appropriate volume  of sample (approximately 25%
         larger than the desired injection volume)  is drawn
         into the  syringe and the  volume is  adjusted to  the
         exact  value desired  and then  immediately  injected
         over a 5-10 seconds  period onto the  GC/MS  system as
         described  in  Section 11.2.3.

13.2  Preparation  of Spiked  Cartridges by Vapor Phase  Injection
     13.2.1  This process involves preparation of a dilution
             bottle containing the desired concentrations
             of the compound(s) of interest as described
             in 13.1 and injecting the desired volume  of
             vapor into a flowing inert gas stream directed
             through a clean Tenax cartridge.
      13.2.2 A helium purge  system is assembled wherein
             the helium flow 20-30 mL/minute is passed
             through a stainless steel Tee fitted with
             a septum injector.   The clean Tenax cartridge
             is connected downstream of the tee using
             appropriate Swagelok fittings.  Once the  cartridge
             is placed in the flowing gas stream the appropriate
             volume vapor standard, in the dilution bottle,
             is injected through the septum as described in
             13.1.6.  The syringe is flushed several times
             by alternately filling the syringe with carrier
             gas and displacing the contents into the  flow
             stream, without removing the syringe from  the septum.
             Carrier flow is maintain through the cartridge  for
             approximately 5 minutes  after injection.

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                               TO!-23

     13.3  Preparation of Spiked Traps Using Permeation or Diffusion
           tubes
           13.3.1  A flowing stream of inert gas containing known
                   amounts of each compound of interest is generated
                   according to ASTM Method 03609(6).  Note that
                   a method of accuracy maintaining temperature
                   within + 0.1°C is required and the system
                   generally must be equilibrated for at least
                   48  hours before use.
           13.3.2  An  accurately  known volume of the standard
                   gas stream (usually 0.1-1 liter) is drawn
                   through a clean Tenax  cartridge using the
                   sampling system described in Section 10.2.1,
                   or  a similar system.   However, if mass flow
                   controllers are employed they must be calibrated
                   for the carrier gas used in Section 13.3.1
                   (usually  nitrogen).   Use of air  as  the  carrier
                   gas for permeation  systems  is not recommended,
                   unless  the compounds  of interest are known
                   to  be highly stable in air.
           13.3.3  The spiked cartridges  are then stored or immediately
                   analyzed as in Section 11.2.4.

14.  Performance Criteria and Quality Assurance

     This section summarizes quality  assurance  (QA) measures and
     provides guidance  concerning  performance criteria  which should be
     achieved within  each laboratory.  In many  cases  the  specific
     QA procedures have been  described  within  the  appropriate  section
     describing the particular activity (e.g.  parallel  sampling).

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                           T01-24

 14.1    Standard  Opreating  Procedures  (SOPs)
        14.1.1  Each  user should  generate SOPs describing the
               following activities as they are performed
               in their laboratory:
               1) assembly, calibration, and operation of
                  the sampling system,
               2) preparation, handling and storage of Tenax
                  cartridges,
               3) assembly and operation of GC/MS system including
                  the thermal desorption apparatus and data
                  system, and
               4) all aspects of data recording and processing.
       14.1.2  SOPs should  provide specific stepwise instructions
               and should be readily available to, and understood
               by the laboratory personnel  conducting the
               work.

14.2   Tenax Cartridge  Preparation

       14.2.1   Each batch of Tenax cartridges  prepared (as
               described  in Section 9) should  be checked for
               contamination by analyzing one  cartridge immediately
               after  preparation.   While analysis  can  be accomplished
               by GC/MS, many  laboratories may chose to use
               GC/FID due to logistical and cost considerations.
       14.2.2 Analysis by GC/FID  is accomplished as described
             for GC/MS (Section  11) except for use of FID
             detection.

-------
                         T01-25

      14.2.3  While acceptance criteria can vary depending
              on the components of interest, at a minimum
              the clean cartridge should be demonstrated
              to contain less than one fourth of the minimum
              level of interest for each component.  For
              most compounds the blank level should be less
              than 10 nanograms per cartridge in order to
              be acceptable.  More rigid criteria may be
              adopted, if necessary, within a specific laboratory.
              If a cartridge  does not  meet  these acceptance
              criteria the  entire lot  should be  rejected.

14.3   Sample Collection

       14.3.1  During each sampling  event at least  one  clean
               cartridge will  accompany the samples to  the
               field and back to the laboratory, without being
               used for sampling, to serve as a field blank.
               The average amount of material found on the
               field blank cartridge may be subtracted from
               the amount found on the actual samples.  However,
               if the blank level is greater than 25% of the
               sample amount, data for that component must
               be  identified  as suspect.
        14.3.2 During each  sampling event  at least one set
               of  parallel  samples  (two  or more  samples  collected
                simultaneously)  will be collected,  preferably
                at  different flow rates as  described  in  Section
                10.1.  If agreement  between parallel  samples
                is  not generally within + 25% the user  should
                collect parallel samples on a much more frequent
                basis (perhaps for all  sampling points).   If
                a trend of lower apparent concentrations with
                increasing flow rate is observed for a set

-------
                           TOT-26
                of parallel  samples one should consider using
                a reduced flow rate and longer sampling interval
                if possible.   If this  practice does  not improve
                the reproducibility further  evaluation  of  the
                method  performance  for the compound  of  interest
                may be  required.
        14.3.3   Backup  cartridges (two cartridges in series)
                should  be  collected  with each  sampling  event.
                Backup  cartridges should contain less than
                20% of  the amount of components of interest
                found in the front cartridges, or be equivalent
                to  the  blank cartridge level, whichever is
                greater.  The frequency of use of backup cartridges
                should  be increased if increased flow rate
                is  shown to yield reduced component levels
               for parallel  sampling.   This  practice will
               help to identify problems arising from breakthrough
               of the component of  interest  during  sampling.

14.4   GC/MS Analysis

       14.4.1   Performance criteria for MS tuning and mass
               calibration have  been discussed in Section
               11.2 and Table  2.  Additional  criteria may
               be used  by  the  laboratory if  desired.  The
               following sections provide performance guidance
               and  suggested criteria  for determining the
               acceptability of  the  GC/MS system.
       14.4.2   Chromatographic efficiency should be evaluated
               using  spiked Tenax cartridges since this practice
               tests the entire system.  In general a reference
               compound  such as perfluorotoluene should be
               spiked onto a cartridge at the 100 nanogram
               level as described in Section  13.2 or 13.3.
              The cartridge is then analyzed by GC/MS as

-------
                  TO!-27
      described in Section 11.4.  The perfluorotoluene (or
      other reference compound) peak is then plotted on an
      expanded time scale so that its width at 10% of the
      peak can be calculated, as shown in Figure 6.  The
      width of the peak at 10% height should not exceed
      10 seconds.  More stringent criteria may be required
      for certain applications.  The assymmetry factor
      (See Figure 6) should be between 0.8 and 2.0.  The
      assymmetry factor for any polar or reactive compounds
      should  be determined using the process described above,
      If peaks are observed that exceed the peak width or
      assymmetry factor criteria above, one should  inspect
      the entire system to determine if unswept zones or
      cold  spots are present  in any of the  fittings and
       is necessary.   Some laboratories may chose
       to evaluate column performance separately by
       direct injection of a test mixture onto the
       GC column.  Suitable schemes for column evaluation
       have been reported in the literature (7).
       Such schemes  cannot be conducted by placing
       the substances onto Tenax because many of
       the compounds (e.g. acids, bases, alcohols)
       contained in  the test mix are not retained,
       or degrade, on Tenax.
14.4.3 The  system  detection  limit for  each  component
        is  calculated from the data  obtained for
        calibration standards.   The  detection  limit
        is defined as

                DL = A + 3.3S

-------
                     T01-28
 where

         DL is the calculated detection limit in
            nanograms injected.
         A is the intercept  calculated  in  Section
            12.1.1  or 12.1.3.
         S is the standard deviation  of replicate
            determinations of  the  lowest level standard
            (at  least three  such determinations  are
            required.
         In  general the detection  limit should be 20
         nanograms or less and for many applications
         detection limits of 1-5 nanograms may be required.
         The  lowest level standard should yield a signal
         to noise ratio, from the total ion current response
         of approximately 5.
14.4.4   The relative standard deviation for replicate
         analyses of cartridges spiked at approximately
         10 times the detection limit  should be 20%
        or less.  Day to day relative standard deviation
        should be 25% or less.
14.4.5  A useful performance evaluation step is  the
        use of an internal standard to  track system
        performance.   This is  accomplished by spiking
        each cartridge,  including  blank, sample, and
        calibration cartridges with approximately  100
        nanograms of  a compound not generally present
        in ambient air (e.g. perfluorotoluene)..  The
        integrated ion intensity for  this  compound
        helps  to identify problems with a  specific
        sample.   In general the user  should calculate
        the standard  deviation of the internal standard
        response  for  a given set of samples analyzed
        under  identical tuning and calibration conditions.
       Any sample giving a value greater than + 2
        standard deviations from the mean (calculated

-------
           T01-29
excluding that particular sample) should be
identified as suspect.  Any marked change 1n
Internal standard response may Indicate a need
for instrument recall oration.

-------
                                  T01-30

                                REFERENCES


1.   Krost, K. J., Pellizzari, E. D., Walburn, S. G., and Hubbard, S. A.,
      Collection and Analysis of Hazardous Organic Emissions",
     Analytical Chemistry. 54, 810-817, 1982.

2.   Pellizzari, E. 0. and Bunch, J. E., "Ambient Air Carcinogenic Vapors-
     Improved Sampling and Analytical Techniques and Field Studies",
     EPA-600/2-79-081, U.S. Environmental  Protection Agency, Research
     Triangle Park, North Carolina,  1979.

3.   Kebbekus, B. B.  and Bozzelli, J. W.,  "Collection  and Analysis of
     Selected Volatile Organic Compounds in Ambient Air", Proc  Air
     Pollution Control Assoc., Paper No. 82-65.2.   Air Poll.  Control
     Assoc., Pittsburgh, Pennsylvania,  1982.

4.   Riggin, R.  M., "Technical Assistance  Document for Sampling  and
     inalyo^ °M Iox!c Or9an1c Compounds in Ambient Air", EPA-600/
                                  Protection  Agency, Research
     Walling, J  F.,  Berkley,  R.  E.,  Swanson,  D.  H., and Toth, F. J.
     EPAm600/7 M^°!iJ"fi0XS ?rgan1C  ChemJ"l-Applications to Tenax",
     EPA-600/7-54-82-059,  U.S.  Environmental Protection Agency, Research
     Triangle Park, North  Carolina, 1982.

     Annual  Book of ASTM Standards, Part 11.03, "Atmospheric Analysis"
     American Society for  Testing  and Material, Philadelphia,         '
     Pennsylvania.

     Grob,  K., Jr., Grob,  6.,-and  Grob, K., "Comprehensive Standardized
     ?U?J   ?JoSt °r Gl3SS CaP111ary Columns", J. Chromatog., 156,
     I —20,

-------
                             TO!-31



 TABLE  1.   RETENTION  VOLUME  ESTIMATES  FOR COMPOUNDS ON TENAX
                                      ESTIMATED RETENTION  VOLUME  AT

        COMPOUND                      IQO'F (38°C)-LITERS/GRAM




                                                   19
Benzene

                                                   97
Toluene


Ethyl Benzene                                     20°
Xylene(s)


Cumene

                                                   20
n-Heptane

                                                   40
1-Heptene



                                                    g

Chloroform


Carbon  Tetrachloride


1,2-Dichloroethane                                 10


1,1,1-Trichloroethane                               6

                                                   on

Tetrcchloroethylene

                                                    ?o
Trichloroethylene

                                                    30
 1,2-Dichloropropane

                                                    QO
 1,3-Dichloropropane


 Chlorobenzene


 Bromoform


 Ethyl ene Di bromide                                 60

                                                   300
 Bromobenzene

-------
                            TO!-32
TABLE 2.  SUGGESTED PERFORMANCE CRITERIA FOR RELATIVE
          ION ABUNDANCES FROM FC-43 MASS CALIBRATION
                                    % RELATIVE
       M/E                           ABUNDANCE
        51                          1.8 + 0.5
        69                          100
       100                          12.0+1.5
       119                          12.0+1.5
       131                          35.0+3.5
       169                          3.0 + 0.4
       219                          24.0+2.5
       264                           3.7 + 0.4
       314                           0.25 + 0.1

-------
                             T01-33
                                       Tenax
                                       ~1.5 Grams (6 cm Bed Depth)
                           •GlassWool Plugs
                           • (0.5 cm Long)
Glass Cartridge
(13.5 mm OD x
100 mm Long)
                                                                     \
                          .(a) Glass Cartridge
1/2" to
1/8"
Reducing
                               Glass Wool
                               Plugs
                               (0.5 cm Long)
         1/8" End Cap,
                                              Metal Cartridge
       1/2"       /                          (12.7 mm OD x
       Swagelok  Zjenax                      100 mm Long)
       Fitting      ~i .5 Grams (7 cm Bed Depth)

                            (b)  Metal Cartridge

                  FIGURE 1. TENAX CARTRIDGE DESIGNS

-------
                                             TO!-34
                             Teflon
                             Compression
                             SM!

                               Purge
                               Gas
                             Cavity for •
                             Tanax
                             Cartridge
                             Latch for
                             Compression
                             Seal
                                                        Effluent to
                                                        6-Port Valve
                                                              To GC/MS

                                                              Vent
                                              Liquid
                                              Nitrogen
                                              Coolant
    Ql
                                  (a) Qlass Cartridges (Compression Fit)
Purge
SwagaJok
End Fittings
                                           Tenax
                                           Trap
Heated
Block
                                                       Carrier
                                                       Gas
                                              Liquid
                                              Nitrogen
                                              Coolant
                                (b) Metal Cartridges (Swagelok Fittings)
                       FIGURE 2. TENAX CARTRIDGE DESORPTION MODULES

-------
                                    T01-35
                   Vent
                                                        Couplings
                                                        to Connect
                                                        Tenax
                                                        Cartridge*
                                             1—-D
                                      Mass Flow
                                      Controllers
                                  (a) Mass Flow Control
                      Rotometer
Vent


Dry
Test
Meter








^•B




•BHH








T
L
V
Needle
Valve








Pump



Coupling to
Connect Tenax
Cartridge
                                    (b) Needle Valve Control
                      FIGURE 3. TYPICAL SAMPLING SYSTEM CONFIGURATIONS

-------
                                          TO!-36
                                SAMPLING DATA SHEET
                            (One Sarole Per Data Sheet)
PROJECT:

SITE:
DATE(S) SAMPLED:
LOCATION:
TIME PERIOD SAMPLED:,

OPERATOR:
INSTRUMENT MODEL NO:

PUMP SERIAL NO:	

SAMPLING DATA
CALIBRATED BY:
                       Sample Number:
                 Start  Time:
                                               Stop Time:
Time
1. 	
2.
-in i
3. 	
4.
N.
Dry Gas
Meter
Reading

— ' '


Rotameter
Reading





Flow
Rate,*Q
ml/Min
1



Ambient
Temperature
°C





Barometric
Pressure,
mtnHg


— — — -^— — — — >— __

Relative
Humidity, %





Comments
	



  Total Volume Data**
          Vm  =  (Final -  Initial) Dry Gas Meter Reading, or
             =  Ql  + 0.2 + Q3---O.N
                                   iuuu x (Sampling Hme in Minutes)  =
                                Liters

                                Liters
  **
     Use data from dry gas meter if available.
                    FIGURE 4.  EXAMPLE SAMPLING DATA SHEET

-------
                            TO!-37
      Thermal
      DMorption
      Chamber
                    6-Port High-Temperature
                    Valva
                                Capillary
                                   Gat
                              Chromatograph
                            Mass
                         Spectrometer
 Data
System
Carrier
Gas
       Vent
 Freeze Out Loop
             Liquid
             Nitrogen
             Coolant
               FIGURE 5
. BLOCK DIAGRAM OF ANALYTICAL SYSTEM

-------
                TO!-38
         Asymmetry Factor -
                         AB
Example Calculation:

    Peak Height - DE * 100 mm
    10% Peak Height - BD - 10 mm
    P«ak Width at 10% Peak Height - AC - 23 mm
         AB- 11 mm
         BC *12mm

    Therefore: Asymmetry Factor - ~ -1.1
FIGURE 6.  PEAK ASYMMETRY CALCULATION

-------
                             METHOD T02                  Revision  1.0
                                                         April,  1984

     METHOD FOR THE DETERMINATION  OF  VOLATILE  ORGAN^         IN
         AMBIENT AIR BY CARBON MOLECULAR SIEVE ADSORPTION AND
         GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
1.    Scope

     1.1   This document describes a procedure for collection and
           determination of selected volatile organic compounds
           which can be captured on carbon molecular sieve (CMS)
           adsorbents and determined by thermal desorption GC/MS
           techniques.
     1.2   Compounds which can be determined by this method are
           nonpolar and nonreactive organics having boiling points
           in  the range -15 to +120°C.  However, not all compounds
           meeting these criteria can be determined.  Compounds for
           which the performance of the method has been documented
           are listed  in Table 1.  The method may be extended  to
           other compounds but additional  Validation by the  user
           is  required.  This method  has  bj;en  extensively  used in
           a single  laboratory.   Consequently, its general applicability
           has not  been thoroughly documented.

 2.   Applicable Documents

      2.1   ASTM Standards
            D 1356 Definitions of Terms Related to Atmospheric Sampling
            and Analysis.
            E 355 Recommended Practice for Gas Chromatography Terms
            and Relationships.

      2.2   Other Documents
            Ambient Air Studies (1,2).

             U.S. EPA Technical Assistance
             Document (3).

-------
                                 T02-2
3.   Summary of Method

     3.1   Ambient air is drawn through a cartridge containing ^0.4
           of a carbon molecular sieve (CMS) adsorbent.   Volatile
           organic compounds are captured on the adsorbent while
           major inorganic atmospheric constituents pass through
           (or are only partially retained).  After sampling,  the
           cartridge is returned to the laboratory for analysis.
     3.2   Prior to analysis the cartridge is purged with 2-3 liters of
           pure, dry air (in the same direction as sample flow) to
           remove adsorbed moisture.
     3.3   For analysis the cartridge is heated to 350°-400°C, under
           helium purge and the desorbed organic compounds are
           collected in a specially designed cryogenic trap.   The
           collected organics are then flash evaporated  onto a
           capillary column GC/MS system (held at -70°C).  The
           individual  components are identified and quantified during
           a temperature programmed chromatographic run.
     3.4   Due to the  complexity of ambient air samples, only high
           resolution  (capillary column) GC techniques are
           acceptable  for most applications of the method.

4.   Significance

     4.1   Volatile organic compounds are emitted into the atmosphere
           from a variety of sources including industrial and  commercial
           facilities, hazardous waste storage and treatment facilities,
           etc.   Many  of these compounds are toxic; hence knowledge of
           the concentration of such materials in the  ambient  atmosphere
           is required in order to  determine human health impacts.
     4.2   Traditionally air monitoring methods for volatile organic
           compounds have relied on carbon adsorption  followed by
           solvent desorption and GC analysis.   Unfortunately, such
           methods are not sufficiently sensitive for  ambient  air
           monitoring, in most cases, because only a small portion  of

-------
                               T02-3

          the sample is injected  onto the GC system.   Recently on-line
          thermal desorption methods, using organic polymeric adsorbents
          such as Tenax® GC, have been used for ambient air monitoring.
          The current method uses CMS adsorbents (e.g. Spherocarb®)
          to capture highly volatile organics (e.g. vinyl chloride)
          which are not collected on Tenax®.  The use of on-line thermal
          desorption GC/MS yields a sensitive, specific analysis
          procedure.
5.    Definitions
      (
     Definitions used in this document and any user prepared SOPs should
     be consistent with ASTM D1356 (4).  All abbreviations and symbols
     are defined with this document at the point of use.

6.    Interferences

     6.1   Only compounds having a mass spectrum and GC retention
           time similar to the compound of  interest will interfere
           in the method.  The most commonly encountered interferences
           are structural isomers.
     6.2   Contamination of  the CMS cartridge with the  compound(s)
           of interest can be a problem in  the method.  The user must
           be careful in the preparation, storage, and  handling of the
           cartridges through the  entire  process to minimize  contamination.

-------
                                 T02-4
7.   Apparatus

     7.1    Gas Chromatograph/Mass Spectrometry system -  must be capable
           of subambient temperature programming.   Unit  mass resolution
           to 800 amu.   Capable of scanning  30-300  amu region every
           0.5-0.8 seconds.   Equipped with data  system for  instrument
           control  as well  as data acquisition,  processing  and storage.
     7.2    Thermal  Desorption Injection  Unit - Designed  to  accommodate
           CMS cartridges in  use (See Figure 3)  and including cryogenic
           trap (Figure  5)  and injection  valve (Carle  Model  5621
           or equivalent).
     7.3    Sampling System  -  Capable of  accurately  and precisely
           drawing  an air flow of 10-500  ml/minute  through  the  CMS
           cartridge.  (See Figure 2a or  b.)
     7.4    Dewar flasks  - 500 ml and 5 liter.
     7.5    Stopwatches.
     7.6    Various  pressure regulators and valves -  for  connecting
           compressed  gas cylinders  to GC/MS  system.
     7.7    Calibration gas -  In  aluminum  cylinder.   Prepared  by
           user or  vendor.  For  GC/MS calibration.
     7.8    High pressure  apparatus for preparing calibration  gas
           cylinders  (if  conducted by user).   Alternatively, custom
           prepared gas mixtures  can  be purchased from gas  supply
           vendors.
     7.9    Friction top can (e.g. one-gallon paint can) - With layer
           of activated charcoal  to  hold clean CMS cartridges.
     7.. 10  Thermometer -  to record ambient temperature.
     7.11  Barometer (optional).
     7.12  Dilution bottle - Two-liter with septum cap for standard
          preparation.
     7.13  Teflon stirbar -  1  inch long
     7.14  Gas tight syringes  - 10-500 ul  for standard  injection onto
          GC/MS system and CMS cartridges.
     7.15  Liquid microliter syringes - 5-50  uL for  injecting neat
         liquid standards into dilution  bottle.
    7.16 Oven  - 60 + 5°C for equilibrating dilution bottle.

-------
                                T02-5
    7.17  Magnetic stirrer.
    7.18  Variable voltage transformers - (120 V and 1000 VA) and
          electrical connectors (or temperature controllers) to
          heat cartridge and cryogenic loop.
    7.19  Digital pyrometer - 30 to 500°C range.
    7.20  Soap bubble flow meter - 1, 10 and 100 ml calibration
          points.
    7.21  Copper tubing (1/8 inch) and fittings for gas inlet lines.
    7.22  GC column - SE-30 or  alternative coating, glass capillary
          or fused silica.
    7.23  Psychrometer (optional).
    7.24  Filter holder - stainless steel or aluminum (to accommodate
          1 inch diameter filter).  Other sizes may be used if
          desired,  (optional)

8.   Reagents  and Materials

     8.1   Empty CMS cartridges -  Nickel  or  stainless  steel  (See
           Figure 1).
     8.2   CMS Adsorbent,  60/80 mesh- Spherocarb® from Analabs Inc.,
           or equivalent.
     8.3   Glasswool - silanized.
     8.4   Methylene chloride - pesticide quality, or equivalent.
     8.5   Gas purifier cartridge for purge  and GC carrier gas
           containing charcoal, molecular sieves, and a drying
           agent.  Available from various chromatography supply
           houses.
     8.6   Helium - Ultra pure, (99.9999%) compressed gas.
     8.7   Nitrogen - Ultra pure, (99.9999%) compressed gas.
     8.8   Liquid nitrogen or argon (50 liter dewar).
     8.9   Compressed air, if required - for operation of GC oven
           door.
     8.10  Perf1uorotributyl amine (FC-43) for GC/MS calibration.
  "   8.11  Chemical Standards - Neat compounds of interest.  Highest
           purity available.

-------
                                 T02-6
9.   Cartridge Construction and Preparation

     9.1    A suitable cartridge design in shown in Figure 1.   Alternate
           designs have been reported (1) and are acceptable, provided
           the user documents their performance.   The design  shown in
           Figure 1 has a built-in heater assembly.   Many users may
           choose to replace this heater design with a suitable
           separate heating block or oven to simplify the cartridge
           design.
     9.2   The cartridge is assembled as shown in Figure 1  using
           standard 0.25 inch O.D. tubing (stainless steel  or nickel),
           1/4 inch to 1/8 inch reducing unions,  1/8 inch nuts,
           ferrules, and endcaps.   These parts are rinsed with
           methylene chloride and heated at 250°C for 1  hour  prior
           to assembly.
     9.3   The thermocouple bead is fixed to the  cartridge  body, and
           insulated with a layer of Teflon tape.  The heater wire
           (constructed from a length of thermocouple wire) is wound
           around the length of the cartridge and  wrapped with Teflon
           tape to secure the wire in place.   The  cartridge is then
           wrapped with  woven silica fiber insulation (Zetex   or
           equivalent).   Finally the entire assembly is  wrapped with
           fiber glass  tape.
     9.4    After assembly one end  of the cartridge is marked  with
           a  serial  number to designate  the cartridge inlet during
           sample collection.
     9.5    The cartridges are then packed  with  ^0.4  grams .of  CMS
           adsorbent.  Glasswool plugs (-vO.5  inches  long) are placed
           at each end of the cartridge  to  hold the  adsorbent firmly
           in place.  Care must  be taken  to insure that  no strands
           of glasswool  extend outside the  tubing, thus  causing
           leakage in the compression endfittings.   After loading the
           endfittings  (reducing unions  and end caps)  are tightened
           onto  the cartridge.

-------
                         T02-7
9.6   The cartridges are conditioned  for  initial  use  by heating
      at 400°C overnight (at least 16 hours) with a 100 mL/minute
      purge of pure nitrogen.  Reused cartridges need only to be
      heated for 4 hours and should be reanalyzed before use to
      ensure complete desorption of impurities.
9.7   For cartridge conditioning ultra-pure nitrogen gas is passed
      through a gas purifier to remove oxygen.moisture and organic
      contaminants.  The nitrogen supply is connected to the
      unmarked end of the cartridge and the flow adjusted to
      •v50 mL/minute using a  needle valve.  The gas flow from the
      inlet  (marked) end of  the cartridge  is vented  to the atmosphere.
 9.8   The cartridge thermocouple  lead  is connected to  a pyrometer
      and the  heater lead is connected to  a  variable voltage
      transformer (Variac)  set at 0  V.   The  voltage  on  the Variac
       is increased to  ^15 V  and adjusted over  a  3-4  minute period
       to stabilize the cartridge  temperature at  380-400°C.
 9.9   After 10-16 hours of  heating (for  new cartridges)  the
       Variac is turned off  and the cartridge is  allowed to  cool
       to <30°C, under continuing  nitrogen  flow.
 9.10  The exit end of the cartridge is capped  and then the entire
       cartridge is removed from the flow line  and the other endcap
       immediately installed.  The cartridges are then placed in a
       metal friction top (paint)  can containing ^2  inches of gran-
       ulated activated charcoal  (to prevent contamination of the
       cartridges during storage) in the bottom, beneath a retaining
       screen.  Clean paper  tissues  (e.g.  Kimwipes ) are placed  in
       can to avoid damage to  the cartridges during  shipment.
  9.11  Cartridges  are stored in the metal  can at all  times except
       when  in  use.  Adhesives initially present in  the cartridge
        insulating  materials  are "burnt off"  during initial condition-
        ing.  Therefore, unconditioned  cartridges should not be placed
        in the  metal can since they may contaminate the other
        cartridges.
  9.12  Cartridges are  conditioned within two weeks of use.   A blank
        from each set  of cartridges is  analyzed prior to use  in  field

-------
                               T02-8
            sampling.  If an acceptable blank level  is achieved,  that
            batch of cartridges (including the cartridge serving  as  the
            blank) can be used for field sampling.
10.   Sampling

     10.1   Flow Rate and  Total  Volume  Selection

           10.1.1    Each  compound  has  a  characteristic retention
                    volume  (liters of  air per unit weight of
                    adsorbent).  However, all Of the compounds listed
                    in Table 1 have retention volumes (at 37°C) in
                   excess of 100 liters/cartridge (0.4 gram CMS
                   cartridge) except vinyl chloride for which the
                   value is *30 liters/cartridge.   Consequently,  if
                   vinyl  chloride  or similarly volatile  compounds are
                   of concern the  maximum allowable  sampling  volume
                   is approximately  20 liters.   If such  highly  volatile
                   compounds  are not of  concern, samples  as large as
                   100 liters  can  be collected.
          10.1.2    To calculate the maximum allowable sampling flow
                   rate the following  equation can be used:
                       ^ax-
         where
                  QMax 1s the calculated maximum sampling
                       rate in mL/minute.
                  t    is the desired sampling  time  in  minutes.
                  VMax 1s the maximum allowable total volume
                       based  on  the  discussion  in  10.1.1.

         10.1.3    For  the cartridge  design shown in Figure 1 QMax
                  should  be between  20 and 500 mL/minute.  If QMax
                  lies outside this  range the sampling time or total
                  sampling volume must be adjusted so that this
                 criterion is achieved.

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                         T02-9
     10.1.4   The flow rate calculated in 10.1.3 defines the
              maximum allowable flew rate.  In general, the
              user should collect additional samples in parallel,
              at successive 2- to 4-fold lower flow rates.  This
              practice serves as a quality control procedure to
              check on component breakthrough and related sampling
              and adsorption  problems, and  is further  discussed
              in the  literature  (5).

10.2  Sample Collection

      10.2.1   Collection of an accurately known volume of air
               is critical to the accuracy of the results.  For
               this reason the use of mass flow controllers, rather
               than conventional needle valves or orifices is highly
               recommended, especially at low flow rates  (e.g.  less
               than 100 milliliters/minute).  Figure 2a illustrates
               a sampling system based on mass flow controllers
               which  readily  allows for  collection of  parallel samples.
               Figure 2b  shows  a commercially available sampling  system
               based  on  needle  valve  flow controllers.
       10.2.2   Prior  to  sample  collection the  sampling flow rate  is
                calibrated near the value used  for sampling, with  a
                "dummy"  CMS cartridge  in  place.   Generally calibration
                is  accomplished using  a soap bubble flow meter  or
                calibrated wet test meter connected to the flow exit,
                assuming the entire flow system is sealed.  ASTM
                Method D 3686 (4) describes an appropriate calibration
                scheme, not requiring a sealed flow system downstream
                of the pump.
        10.2.3   The flow  rate should  be  checked  before and  after  each
                sample collection.  Ideally, a  rotemeter  or mass  flow
                meter should  be  included in  the  sampling  system to
                allow periodic  observation  of  the flow rate without
                 disrupting  the  sampling  process.

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                    T02-10

 10.2.4   To collect an air sample the cartridges are removed
          from the sealed container just prior to initiation  of
          the collection process.
.10.2.5   The exit (unmarked)  end  of the cartridge is  connected
          to the sampling apparatus.   The endcap  is left on the
          sample inlet and the entire system is leak checked by
          activating the sampling  pump and  observing that no flow
          is  obtained  over a 1 minute period.   The sampling
          pump is then shut  off.
 10.2.6   The endcap is removed  from  the cartridge, a  particulate
          filter and holder  are  placed  on the  inlet end of the
          cartridge, and the sampling  pump  is  started.  In many
          situations a particulate  filter is not  necessary since
          the compounds of interest are  in  the vapor state.  How-
          ever,  if,  large amounts of particulate matter are
          encountered, the filter may be  useful to prevent con-
          tamination of the  cartridge.  The following  parameters
          are recorded on an appropriate data sheet (Figure 4):
          date,  sampling location, time, ambient  temperature,
          barometric  pressure, relative humidity, dry gas meter
          reading  (if applicable), flow rate,  rotometer reading
          (if applicable), cartridge number, pump, and dry gas
          meter  serial  number.
10.2.7    The samples  are collected for the desired time,
          periodically recording the variables listed above.   At
          the end of  the sampling period the parameters listed
          in  10.2.6 are  recorded and the flow  rate is checked.
          If  the flows at the beginning and end of the  sampling
          period differ by more than 10%, the  cartridge should
          be  marked as suspect.
10.2.8    The cartridges are removed (one at a time),  the
          endcaps are  replaced, and the cartridges are  placed
          into the original container.  The friction top can
          is  sealed and packaged for immediate shipment to  the
         analytical laboratory.

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                  102-11

10.2.9   The average sample rate is calculated and recorded
         for each cartridge according to the following equation:
where
         Q. = Average flow rate in ml /minute.
         0, , Q2,...QN = Flow rates determined
         beginning, end, and immediate points
         during sampling.
         N = Number of points averaged.
10.2.10  The total volumetric flow is obtained directly from
         the dry gas meter or calculated and recorded for
         each cartridge using the following equation:
                      TxQ.
                 V  =
                  m
where
     1UOTJ
         V  = Total volume sampled in liters at measured
          m
              temperature and pressure.
         T  = Sampling time = T2-T-j, minutes.

 10.2.11  The total volume sampled  (Vs) at standard conditions,
         760 mm Hg and 25°C, is calculated from the following
         equation:
Vs = Vm x 760 x 273
                                       ta
where
                  Pa =  Average barometric  pressure, mm Hg
                  ta =  Average ambient  temperature,  °C.

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                             T02-12

11.   Sample Analysis

     11.1   Sample  Purging

           11.1.1   Prior to  analysis  all  samples are purged at room
                   temperature with pure, dry air or nitrogen to remove
                   water vapor.  Purging  is accomplished as described
                   in 9.7 except that the gas flow is in the same direction
                   as sample flow  (i.e. marked end of cartridge is
                   connected to the flow system).
           11.1.2   The sample is purged at 500 mL/minute for 5 minutes.
                   After purging the endcaps are immediately replaced.
                   The cartridges are returned to the metal can or
                   analyzed immediately.
         11:1.3    If very humid air is being sampled the purge time
                  may be increased to more efficiently remove water
                  vapor.   However, the sum of sample volume  and  purge
                  volume  must be less than 75% of the retention volume for
                  the most volatile component of interest.

   11.2  GC/MS Setup

         11.2.1    Considerable  variation  from one laboratory  to another
                  is expected in terms  of instrument configuration.
                  Therefore, each  laboratory must be responsible for
                  verifying  that their  particular system yields satis-
                  factory results.  Section 14 discusses specific
                  performance criteria which should be met.
        11.2.2    A block diagram of the analytical system required
                  for analysis of CMS cartridges is depicted in Figure 3.
                  The thermal desorption system must be designed to
                  accommodate the particular cartridge configuration.
                  For the CMS cartridge design shown in Figure 1, the
                  cartridge heating is accomplished as described in 9.8.
                 The use of a desorption  oven,  in conjunction with  a

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                     T02-13
        simplier cartridge design  is  also  acceptable.   Exposure
        of  the  sample to  metal  surfaces  should  be minimized  and
        only stainless steel  or nickel should be employed.
        The volume of tubing  leading  from  the cartridge to
        the GC  column must be minimized  and  all areas must
        be  well-swept by  helium carrier  gas.
11.2.3  The GC  column oven must be capable of being  cooled  to
        -70°C and subsequently temperature programmed to 150°C.
11.2.4  The specific GC column and temperature  program  employed
        will be dependent on  the compounds of  interest.  Appro-
        priate  conditions are described  in the  literature (2).
        In  general, a nonpolar stationary phase (e.g. SE-30,
        OV-1) temperature programmed  from -70  to  150°C  at 8°/
        minute will be suitable.  Fused  silica, bonded-phase
        columns are preferable to glass  columns since they are
        more rugged and can  be inserted  directly into the MS
        ion source, thereby eliminating  the  need for a  GC/MS
        transfer line.  Fused silica  columns are also more
        readily connected to the GC injection  valve (Figure 3).
        A drawback of fused silica, bonded-phase columns is the
        lower  capacity compared to coated, glass capillary
        columns.   In most cases the column capacity will be less
        than 1 microgram injected for fused silica columns.
11.2.5  Capillary  column dimensions of 0.3 mm ID and 50 meters
        long are generally appropriate although shorter lengths
        may be sufficient in many cases.
11.2.6  Prior  to  instrument  calibration or sample analysis  the
        GC/MS  system  is  assembled as shown in Figure 3.  Helium
        purge  flow (through  the cartridge) and carrier  flow are
        set at approximately 50 mL/minute and 2-3 mL/minute
        respectively.  When  a  cartridge is not in place a union
        is  placed  in  the helium purge line to ensure a  continuous
        inert  gas  flow through  the injection loop.

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                            T02-14

       11.2.7   Once the column and other  system components  are  assembled
                and the various flows  established the  column temperature
                is  increased  to 250°C  for  approximately  four hours  (or
                overnight if  desired)  to condition  the column.
       11.2.8   The MS  and data system are set  up according  to the
                manufacturer's  instructions.  Electron impact ionization
                (70eV)  and an electron multiplier gain of approximately
                5 x 10   should  be  employed.  Once the  entire GC/MS
                system  has  been  setup  the  system  is calibrated as described
                in  Section  11.3.   The  user should prepare a detailed
                standard  operating procedure (SOP) describing this process
                for the  particular instrument being used.


11.3  GC/MS Calibration
      11.3.1    Tuning and mass  standardization  of the  MS system  is per-
               formed according to manufacturer's instructions
               and  relevant user prepared  SOPs.   Perfluorotributyl amine
               (FC-43)  should generally be employed as the reference
               compound.   The material  is  introduced directly into the
               ion  source through  a molecular leak.  The instrumental
               parameters (e.g., lens  voltages, resolution, etc.)
               should be  adjusted  to give  the relative ion abundances
               shown  in  Table 2, as well as acceptable resolution and
               peak shape.  If  these approximate  relative abundances
               cannot be  achieved, the  ion source may  require cleaning
               according  to manufacturer's instructions.   In the event
               that the user's instrument cannot achieve these relative
               ion  abundances, but is otherwise operating properly,
               the  user may adopt another set of relative abundances
               as performance criteria.  However, these alternate
               values must be repeatable on a day-to-day basis.

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                   T02-15

11.3.2   After the mass standardization and tuning  process  has
         been completed and the appropriate values  entered  into
         the data system, the user should then calibrate the
         entire GC/MS system by introducing known quantities
         of the components of interest into the system.   Three
         alternate procedures may be employed for the calibra-
         tion process including 1) direct injection of dilute
         vapor phase standards, prepared in a dilution bottle
         or compressed gas cylinder, onto the GC column,
         2) injection of dilute vapor phase standards into  a
         flowing inert gas stream directed onto a CMS cartridge,
         and 3) introduction of permeation or diffusion tube
         standards onto a CMS cartridge.  Direct injection  of a
         compressed gas cylinder  (aluminum) standard containing
         trace levels of the compounds of interest  has been found
         to be the most convenient practice since such standards
         are stable over a several month period.  The standards
         preparation processes for the various approaches are
         described in Section 13.  The following paragraphs
         describe the instrument  calibration process for these
         approaches.
 11.3.3   If the system is to be calibrated by direct injection
         of a  vapor phase standard, the  standard, in either a
         compressed gas  cylinder  or dilution flask, is obtained
         as described  in  Section  13.  The MS and data system
         are  setup for acquisition, but  the ionizer filament
         is shut  off.  The GC column  oven  is cooled to -70°C,
         the  injection valve is placed  in  the  load mode, and the
         cryogenic loop  is immersed in  liquid  nitrogen or liquid
         argon.   Liquid  argon  is  required  for  standards  prepared
         in nitrogen or  air, but  not  for standards prepared  in
         helium.  A  known  volume  of the  standard (10-1000 ml)
         is  injected through the  cryogenic  loop  at a  rate of
         10-100  mL/minute.

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                    T02-16

 11.3.4   Immediately after loading  the vapor  phase  standard,  the
          injection  valve  is  placed  in  the  inject mode,  the GC
          program and system  clock are  started, and  the  cryogenic
          loop  is heated to 60°C  by  applying voltage  (15-20 volts)
          to  the  thermocouple wire heater surrounding the loop.
          The voltage is adjusted to maintain a loop temperature
          of  60°C.   An automatic temperature controller can be
          used  in place of  the manual control system.  After
          elution of unretained components  «3 minutes after
          injection)  the ionizer filament is turned on and data
          acquisition is initiated.  The helium purge line (set
          at  50 mL/minute)  is connected to the injection valve
          and the  valve is  returned to the load mode.  The loop
          temperature is increased to 150°C, with helium  purge,
          and held at this temperature until the next sample is
          to be loaded.
11.3.5   After the last component of interest  has  eluted,
         acquisition is terminated and  the  data is  processed  as
         described in Section 11.3.8.   The  standard  injection
         process  is  repeated  using different standard  concentra-
         tions  and/or volumes to  cover  the  analytical  range of
         interest.
11.3.6   If  the  system is  to be  calibrated by  analysis  of
         standard CMS cartridges,  a  series  of cartridges is
         prepared as described in  Sections  13.2 or 13.3.  Prior
         to analysis the cartridges  are  stored  (no longer than
         48 hours) as described in Section  9.10.  For analysis
         the  injection valve  is placed  in the load mode and the
         cryogenic loop is  immersed  in  liquid nitrogen (or
         liquid argon if desired).  The  CMS cartridge is installed
         in the helium purge line (set at 50 mL/minute) so that
         the  helium  flow through the cartridge is opposite to
         the  direction of sample flow and the purge gas is
         directed  through the cryogenic loop and vented to the

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                       T02-17

             atmosphere.  The CMS cartridge is heated to 370-400°C
             and maintained at this temperature for 10 minutes (using
             the temperature control process described in Section 9.8).
             During  the desorption period, the GC column oven is
             cooled  to  -70°C and the MS and data system are setup for
             acquisition, but the ionizer filament is turned off.
     11.3.7   At the  end of the 10 minute desorption period, the ana-
             lytical process described  in Sections 11.3.4 and 11.3.5
             is conducted.  During  the  GC/MS analysis heating of the
             CMS cartridge  is discontinued.  Helium flow is maintained
             through the  CMS cartridge  and  cryogenic  loop until the
             cartridge has  cooled to  room  temperature.  At  that time,
              the cryogenic  loop  is  allowed  to  cool to room  temperature
             and the system is  ready  for further cartridge  analysis.
              Helium flow is  maintained  through the cryogenic  loop  at
              all times, except  during the  installation  or  removal  of
              a CMS cartridge,  to minimize  contamination of the  loop.
     11.3.8   Data processing for instrument calibration involves
              determining retention times,  and integrated  characteristic
              ion intensities for each of the compounds  of interest.
              In addition, for at least one chromatographic run, the
              individual mass spectra should be inspected and compared
              to reference spectra to ensure proper instrumental
              performance.  Since the steps involved in data processing
              are highly instrument specific,,  the user should prepare
              a SOP  describing the process  for individual use.  Overall
              performance criteria for  instrument calibration are
              provided  in Section 14.   If these criteria are not
              achieved, the user should refine the instrumental
              parameters and/or operating procedures  to meet these
              criteria.

11.4  Sample Analysis

      11.4.1   The sample  analysis  is  identical to that described
               in Sections  11.3.6  and  11.3.7 for the analysis  of
               standard CMS cartridges.

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                              T02-18

            11.4.2   Data  processing for sample data generally involves
                    1) qualitatively determining the presence or absence
                    of each component of interest on the basis of a set
                    of characteristic ions and the retention time using
                    a reversed-search software routine, 2) quantification
                    of each identified component by integrating the intensity
                    of a characteristic ion and comparing the value to
                    that of the calibration standard,  and 3) tentative
                    identification of other components  observed using a
                    forward (library)  search software  routine.   As  for
                   other user specific processes,  a SOP should be  prepared
                   describing the specific operations  for each  individual
                   laboratory.

12.   Calculations

     12.1   Calibration Response  Factors
           12.1.1   Data  from  calibration standards is  used  to calculate a
                   response factor for each component  of interest.
                   Ideally the process involves analysis of at least three
                   calibration levels of each component during a given
                   day and determination of the response factor (area/
                   nanogram injected) from the linear  least squares
                   fit of a plot of nanograms injected versus area
                   (for the characteristic ion).  In general, quantities
                  of components greater than 1,000 nanograms should not
                  be injected because of column overloading and/or MS
                  response nonlinearity.
          12.1.2  In practice the daily routine may not always allow
                  analysis of three  such  calibration  standards.   In
                  this  situation calibration  data  from consecutive days
                  may be pooled  to yield  a response factor, provided
                  that  analysis  of replicate  standards of the  same
                  concentration  are shown  to  agree  within 20*  on  the
                  consecutive days.   In all cases one  given standard

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                      T02-19

            concentration, near the midpoint of the analytical
            range of interest, should be injected at least once
            each day to determine day-to-day precision of response
            factors.

     12.1.3 Since substantial nonlinearity may be present in the
            calibration curve, a nonlinear least squares fit
             (e.g. quadratic)  should be employed.  This process
            involves fitting  the data to the following equation:
     where
                        Y = A + BX  + CX2
             Y = peak area
             X - quantity of component injected  nanograms
             A, B, and C are coefficients in the equation.
12.2  Analyte Concentrations

      12.2.1   Analyte quantities  on  a  sample  cartridge  are  calculated
              from the following  equation:

                         YA = A + BXA  + CX2

      where   Y. is the area of the  analyte characteristic  ion for
               M
                the sample cartridge.
              XA is the calculated quantity of analyte on the sample
                cartridge, in nanograms.
              A, B, and C are the coefficients calculated from the
                calibration curve described in Section 12.1.3.
      12.2.2  If instrumental response is essentially linear over the
              concentration range of interest, a linear equation
              (C=0 in the equation above) can be employed.

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                              T02-20
            12.2.3   Concentration of analyte in the original air sample
                    is calculated from the following equation:
           where
                   CA is the calculated concentration of analyte in ng/L.

                   Vs and XA are as previously defined in Section 10.2.11
                   and 12.2.1, respectively.

13.   Standard Preparation

     13.1   Standards  for Direct Injection

           13.1.1   Standards  for direct injection can be  prepared in
                   compressed  gas cylinders or in dilution vessels.
                   The dilution flask protocol has been described in
                   detail in another method and is not repeated here (6).
                   For the CMS method where only volatile compounds
                   (boiling point <120°C) are of concern, the preparation
                  of dilute standards in 15 liter aluminum compressed
                  gas cylinders has been found to be most convenient.
                  These standards are generally stable over at least a
                  3-4 month period and in some cases can be purchased
                  from commercial  suppliers on a  custom prepared basis.
          13.1.2  Preparation of compressed gas cylinders requires
                  working with high pressure  tubing  and fittings, thus
                  requiring a user  prepared SOP which ensures  that
                  adequate  safety precautions  are taken.   Basically,
                  the preparation process  Involves injecting a  pre-
                  determined  amount of neat liquid or gas  into  an
                  empty  high  pressure cylinder of known volume, using
                  gas flow  into the cylinder to complete the transfer.

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                            T02-21

                  The cylinder is then pressurized to a given value
                  (500-10QO psi).  The final cylinder pressure must be
                  determined using a high precision gauge after the
                  cylinder has thermally equilibrated for a 1-2 hour
                  period  after filling.
           13.1.2 The  concentration  of components  in the cylinder
                   standard should be determined by comparison with
                   National Bureau of Standards  reference standards
                   (e.g. SRM  1805-benzene  in nitrogen) when  available.
           13.1.3  The theoretical concentration (at 25°C and  760  mm
                   pressure)  for preparation of cylinder standards
                   can be calculated using the following equation:

                             C  = VI x d   14.7      x 24.4 x 1000
                              T   vx Pc + 14.7
           where   CT   is the component concentration, in ng/mL at 25°C
                        and 760 mm Hg pressure.
                   V    is the volume of neat liquid component injected,
                        in yL.
                   Vc  is the  internal  volume  of the cylinder, in  I..
                   d    is the density of  the neat  liquid component,
                        in g/nt.
                    p    is the  final  pressure of the cylinder  standards,
                        in pounds per square inch gauge  (psig).

13.2   Preparation of  Spiked Traps by Vapor  Phase  Injection

       This process  involves preparation of  a dilution flask
       or compressed  gas cylinder containing the desired concentra-
       tions of the  compound(s)  of interest  and  injecting the  desired
       volume of vapor into  a  flowing gas  stream which  is directed
       onto a clean CMS cartridge.  The  procedure is described in
       detail in another method within  the Compendium (6)  and  will  not be
       repeated here.

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                             T02-22

      13.3   Preparation of Spiked Traps Using Permeation or Diffusion Tubes

          .13.3.1  A flowing stream of inert gas containing known amounts
                   of each compound of interest is generated according
                   to ASTM Method D3609 (4).  Note that a method of
                   accurately maintaining temperature within + 0.1°C is
                   required and the system generally must be equilibrated
                   for at least 48 hours before use.
           13.3.2  An accurately known volume of the  standard gas stream
                   (usually 0.1-1  liter)  is drawn through a  clean CMS
                   cartridge using the sampling system described in
                   Section  10.2.1,  or  a similar system.   However, if mass
                   flow controllers are employed,  they must  be  calibrated
                   for  the  carrier  gas used in  Section 13.3.1  (usually
                   nitrogen).   Use  of  air  as  the  carrier  gas  for permeation
                   systems  is not  recommended,  unless  the  compounds  of
                   interest  are  known  to be highly stable  in air.
           13.3.3   The  spiked traps are then  stored or immediately
                   analyzed  as  in Sections  11.3.6 and  11.3.7.

14.   Performance Criteria and Quality  Assurance

     This  section  summarizes the quality assurance (QA) measures  and
     provides  guidance  concerning performance criteria which should  be
     achieved  within each laboratory.   In many  cases the specific QA
     procedures  have been described within  the  appropriate section
     describing  the particular activity (e.g. parallel sampling).

     14.1   Standard Operating Procedures (SOPs)

           14.1.1  Each user should generate SOPs describing the following
                  activities as accomplished in their laboratory:
                  1) assembly,  calibration and operation of the sampling
                  system, 2) preparation,  handling and storage of CMS
                  cartridges,  3) assembly  and operation of 6C/MS system
                  including the thermal desorption apparatus and data
                  system, and 4)  all aspects of data  recording and  processing.

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                       T02-23

      14.1.2   SOPs  should  provide  specific  stepwise  instructions  and
              should be readily  available to,  and  understood  by the
              laboratory  personnel  conducting  the  work.

14.2  CMS Cartridge Preparation

      14.2.1   Each batch  of CMS  cartridges,  prepared as described in
              Section 9, should  be checked  for contamination  by
              analyzing one cartridge, immediately after  preparation.
              While analysis can be accomplished by GC/MS, many
              laboratories may chose to use GC/FID due to logistical
              and cost considerations.
      14.2.2  Analysis by GC/FID is accomplished as described for
              GC/MS  (Section 11) except for use of FID detection.
      14.2.3  While  acceptance criteria can vary depending on the
              components of interest, at a minimum the clean
              cartridge should be  demonstrated to contain less than
              one-fourth of the minimum level of  interest for each
              component.   For most compounds  the  blank level should
              be  less  than  10 nanograms per cartridge in order to be
              acceptable.   More rigid criteria may  be adopted, if
              necessary,  within a  specific laboratory.   If a cartridge
              does not meet these  acceptance  criteria, the entire lot.
              should be  rejected.

 14.3  Sample Collection

       14.3,1  During each sampling event at least one clean  cartridge
               will accompany  the  samples to the field and back  to the
               laboratory, having  been placed in the sampler  but  without
               sampling air, to  serve as a  field blank.   The average
               amount of material  found on  the field blank cartridges
               may be subtracted from the amount found on the actual
               samples.  However,  if the blank level is greater than

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                        T02-24

              25% of the sample amount, data for that component
              must be identified as suspect.
      14.3.2  During each sampling event at least one set of
              parallel samples (two or more samples collected
              simultaneously) should be collected, preferably at
              different flow rates as described in Section 10.1.4.
              If agreement between parallel samples is not generally
              within +25% the user should collect parallel samples
              on a much more frequent basis (perhaps for all  sampling
              points).   If a trend of lower apparent concentrations
              with increasing flow rate is observed for a set of
              parallel  samples  one should consider usvig a reduced
              sampling  rate and longer sampling interval, if  possible.
              If this  practice  does not improve the reproducibility
              further evaluation of the method  performance for the
              compound  of  interest might be required.
      14.3.3  Backup cartridges  (two  cartridges  in  series)  should be
              collected with  each  sampling  event.   Backup cartridges
              should contain  less  than  10%  of the amount  of components
              of interest found in  the  front cartridges,  or be equiva-
              lent to the blank cartridge  level, whichever  is greater.

14.4  6C/MS Analysis

      14.4.1  Performance  criteria for MS tuning and mass standardiza-
              tion  have  been  discussed in Section  11.2 and Table 2.
              Additional criteria  can be used by the laboratory,
              if desired.   The  following sections  provide performance
              guidance  and  suggested  criteria for  determining the
              acceptability of  the GC/MS system.

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                  T02-25
14 4.2  Chromatographic efficiency should be evaluated daily
        by the injection of calibration standards.   A reference
        compound(s) should be chosen from the calibration
        standard and plotted on an expanded time scale so that
        its width at 10* of the peak height can be calculated,
        as shown in Figure 6.  The width of the peak at 10%
        height should  not exceed  10 seconds.  More stringent
        criteria may be  required  for certain applications.
        The  asytrmetry  factor  (see  Figure 6)  should be  between
        0 8  and' 2.0.   The  user should  also  evaluate  chroma-
         tographic  perfonnance for any  polar or  reactive  compounds
         of interest,  using the process described  above.   If  peaks
         are observed that exceed the peak width or asymmetry
         factor criteria above, one should inspect the  entire
         system to determine if unswept zones or cold spots are
                               fittings or tubing  and/or if
                               column  is required.  Some labora-
                               valuate  column performance separately
       present in any of the
       replacement of the GC
       tories may chose to
          by  direct  injection If a test mixture onto the GC
          column.  Suitable  scUes for column evaluation have been
          reported in  the literature  (7).
                              For  each component  is  calculated
                              ed  for  calibration  standards.   The
                              efined as
14.4.3  The detection limit
        from the data obtain
        detection limit is d
                     DL s A + 3.3S

where
        DL is the calculated detection limit in nanograms
           injected.
        A is the intercept  calculated in Section 12.1.3.
        S is the standard deviation  of replicate determina-
            tions of the lowest  level  standard  (at  least  three
            such determinates  are required).   The  lowest

-------
                          T02-26
                level  standard should yield a signal to noise ratio
                (from  the total  ion current response) of approximately 5.
        14.4.4   The relative standard deviation for replicate analyses
                of cartridges spiked at approximately 10 times the
                detection limit should be 20% or less.   Day to day
                relative standard deviation for replicate cartridges
                should be 25% or less.
       14.4.5  A useful performance evaluation  step is  the use  of an
               internal standard to track system performance.   This
               is accomplished  by spiking each  cartridge,  including
               blank,  sample, and calibration cartridges with approx-
               imately 100  nanograms of  a compound  not  generally
               present is ambient air  (e.g. perfluorotoluene).  Spik-
               ing  is  readily accomplished using the procedure outlined
               in Section 13.2,  using a  compressed  gas  standard.  The
               integrated ion intensity  for this compound helps to
               identify problems with a  specific sample.  In general
               the user should calculate  the standard deviation of the
               internal standard response for a given set of samples
               analyzed under identical tuning and calibration conditions.
               Any sample giving a value greater than + 2 standard
               deviations from the mean (calculated excluding that
              particular sample) should  be identified  as  suspect.
              Any marked change in internal  standard response may
              indicate a need  for instrument  recalibration.

14.5  Method Precision and  Recovery

      14.5.1  Recovery and  precision data for selected  volatile organic
             compounds are presented in Table  1.   These data were
             obtained using ambient air, spiked with known amounts
             of the compounds in a dynamic mixing  system (2).
      14.5.2  The data in Table  1 indicate that in  general recoveries
             better than 75% and precision (relative standard
             deviations) of 15-20% can be obtained.  However,
             selected compounds (e.g.  carbon tetrachloride and

-------
          T02-27
benzene) will have poorer precision and/or recovery.
The user must check recovery and precision for any
compounds for which quantitative data are  needed.

-------
                                T02-28

                            References
 1.   Kebbekus,  B.  B.  and J. W.  Bozzelli.   Collection  and  Analysis  of
     Selected Volatile Organic  Compounds  in  Ambient Air.   Proceedings
     of Air  Pollution Control Association, Paper  No.  82-65.2, Air
     Pollution  Control Association,  Pittsburgh, Pennsylvania, 1982.

 2.   Riggin  R.  M.  and L. E. SIivon.  Determination of Volatile Organic
     Compounds  in  Ambient Air Using  Carbon Molecular  Sieve Adsorbants
     Special Report on Contract 68-02-3745 (WA-7), U.S. Environmental
     Protection Agency, Research Triangle  Park, North Carolina, September,
     1983.

 3.   Riggin, R. M., "Technical Assistance Document for Sampling and
     Analysis of Toxic Organic Compounds in Ambient Air", EPA-600/4-
     83-027, U.S.  Environmental Protection Agency, Research Triangle
     Park, North Carolina, 1983.

4.   Annual Book of ASTM Standards,  Part 11.03, "Atmospheric Analysis-
     Occupational  Health and Safety", American Society for Testing and
     Materials, 1983.

5.   Walling, J. F., Berkley,  R. E., Swanson, D.  H., and Toth, F.  J.
     rn^lnli ?!r for Gaseous Organic Chemical-Applications to Tenax",
     EPA-600/7-54-82-059, U.S.  Environmental  Protection Agency,  Research
    Triangle Park, North Carolina, 1982.

6.  This Methods Compendium - Tenax Method (TO 1).

7.  Grob, K.,  Jr., Grob, G.,  and Grob, K., "Comprehensive Standardized
    ?U?ilt:yoJoSt f°r  GlaSS  CaPillary Columns", J. Chromatog., 156
    1-20, 1978.                                              ——

-------
                           TABLE  1   VOLATILE ORGANIC COMPOUNDS FOR WHICH THE
                                    CMS ADSORPTION METHOD HAS BEEN EVALUATED
        Compound
Vinyl Chloride
Acrylonitrile
Vinylidene Chloride
Methylene Chloride
Allyl Chloride
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane
Benzene
Carbon Tetrachloride
To!uene
Retention
Time,/ *
Minutes^'
6.3
10.8
10.9
11.3
11.4
13.8
14.5
14.7
15.4
15.5
18.0
Characteristic
Mass Fragment
Used For
Quantification
62
53
96
84
76
83
62
97
78
117
91
Method Performance -Data^
Concentration,
ng/L
17
20
36
28
32
89
37
100
15
86
4.1
Percent
Recovery
74
85
94
93
72
91
85
75
140
55
98
Standard
Deviation
19
18
19
16
19
12
11
9.1
37
2.9
5.4





o
ro
ro
VO




 a)   GC conditions as follows:
         Column - Hewlett Packard,  crosslinked  methyl  silicone,
                  0.32 mm ID x 50 mm long,  thick  film, fused silica.
                  Temperature Program - 70°C for  2 minutes then  increased at
                                         8°C/minute to 120°C.
 b)  From Reference 2.  For spiked ambient air.

-------
                       T02-30
TABLE 2.  SUGGESTED PERFORMANCE CRITERIA FOR RELATIVE
          ION ABUNDANCES FROM FC-43 MASS CALIBRATION
      M/E
% Relative
Abundance
       51
       69
      100
      119
      131
      169
      219
      264
      314
 1.8 + 0.5
 100
 12.0 + 1.5
 12.0 + 1.5
 35.0 + 3.5
 3.0 + 0.4
 24.0 + 2.5
  3.7 + 0.4
  0.25 + 0.1

-------
                     T02-31
                                     Thermocoupia
                            Zetex
                            I mutation
                           /-Fibarglaa
                          / T«p«
              mnm
             1/4" Nut
                     t
          Radueing
          Union
Stainlan
Staal Tuba
1/4" O.D. x 3" Long
                                           Tharmocoupla
                                           Connector
                                         Haatar
                                         Connector
FIGURE 1. DIAGRAM SHOWING CARBON MOLECULAR SIEVE TRAP (CMS) CONSTRUCTION

-------
                                              T02-32
                      Vtm
                                                              Couplings
                                                              to Connect
                                                              CMS
                                                              Cartridge!
                                      (•) Mm Row Control
                        Rotometer
Vent
Dry
Twt
                                                     Pump
                                                               Coupling to
                                                               Connect CMS
                                                               Cartridge
                                    V§1»»
                                    (b| Needle Valve Control
                  FIGURE  2.   TYPICAL SAMPLING  SYSTEM CONFIGURATIONS

-------
                                       T02-33
              Coupling! for
              CMS Cartridge
                                            . Heated 6-Port
                                             Injection Valve

                                               ,, Cryogenic Loop («et Figurt SI
Htlium Tank
and Regulator
    Flow
    Controlltn
           Liquid Nitrogen
                 Helium Purge
                 From Heated
                 CMS Trap
                 60 ml/minute
                  Helium Purge
                  From Cooling
                  CMS Cartridge
   MMI
Spectrometer
                                         QC Column
                                       Cooling to -70 C

                                    (b) Velvt - Load Mode
                                           Vent
                                          QC Column

                                     (el Valve - Inject Mode
 Cryogenic Trap
 Held at Liquid N2
 Temperature
                                                              Helium Carrier
                                                              Flow - 2-3 ml/minute
   Cryogenic Trap
   Held at 60 C
     FIGURE  3.   GC/MS ANALYSIS  SYSTEM  FOR  CMS  CARTRIDGES

-------
                                          702-3^
PROJECT:,


SITE:
LOCATION:
INSTRUMENT MODEL NO:.


PUMP SERIAL NO:	


SAMPLING DATA
                                SAMPLING DATA SHEET
                            (One Sample Per Data Sheet)
DATE(S) SAMPLED:
TIME PERIOD SAMPLED:


OPERATOR:
CALIBRATED BY:
                       Sample Number:_

                 Start Time:
 Stop Time:
Time
1.
2.
3.
4.
N.
Dry Gas
Meter
Reading





Rotameter
Reading





Flow
Rate,*Q
ml/Min





Ambient
Temperature
°C





Barometric
Pressure,
mmHg





Relative
Humidity, X





Comments





   Total  Volume  Data**
          Vm * (Final - Initial) Dry Gas Meter Reading, or
                Ql + Q2 + Q3---QN
                                    1000 x (Sampling Time in Minutes)
                                 Liters

                                 Liters
    * Flowrate from rotameter or soap bubble calibrator
      (specify which).
   ** Use data from dry gas meter if available.
                     FIGURE  4.  EXAMPLE SAMPLING DATA SHEET

-------
                 T02-35
oq
30
oo
oc
3O-
OC
          1/8" to 1/16" Raduetng Union
          1/8" Swagalok Nut and Farrula
                   Silanizad
                    Glass
                    Wool
                   1/2" Long
         60/80 Mash Silanizad Glass Baads
                                         #
                                         e3
                                         oo
                                          >0
                                          °0
                                          oo
        Stainlass Staal
        Tubing
        1/8" O.D. x 0.08" I.D. x 8" Long
     FIGURE  5.  CRYOGENIC TRAP  DESIGN

-------
             T02-36
                         BC
         Asymmetry Factor • •—•
                         AB
ExampU Calculation:

    Paak Haight - OE • 100 mm
    10% PMk Haight - BO - 10 mm
    Paak Width at 10% Paak Haight «• AC • 23 mm
         AB -11 mm
         BC »12mm
                              12
    Tharafora: Atymmatry Factor - •— «• 1.1
FIGURE 6. PEAK ASYMMETRY CALCULATION

-------
                               METHOD T03                Revision 1.0
                                                         April, 1984
       METHOD FOR THE  DETERMINATION  OF  VOLATILE  ORGANIC  COMPOUNDS
       IN AMBIENT AIR  USING CRYOGENIC PRECONCENTRATION TECHNIQUES
            AND GAS CHROMATOGRAPHY WITH FLAME  IONIZATION AND
                    AND ELECTRON CAPTURE  DETECTION
1.     Scope

      1.1   This document describes a method for the determination  of
            highly volatile compounds having boiling points in the  range
            of -10 to 200°C.
      1.2   The methodology detailed in this document is currently
            employed by numerous laboratories (l-4;8-ll).   Modifications
            to this methodology should be accompanied by appropriate
            documentation of the validity and reliability of these
            changes.

 2.    Applicable Documents

      2.1   ASTM Standards

            D1356  Definition of Terms  Related to Atmospheric Sampling
            and Analysis
            E  355  Recommended  Practice for  Gas  Chromatography Terms
            and Relationships

       2.2   Other  Documents

            Ambient Air Studies  (1-4).
            U. S.  EPA Technical  Assistance  Document (5).

 3.    Summary of  Method

     -  3.1   Ambient air analyses are performed  as  follows.  A collection
             trap,  as illustrated in Figure  1,  is submerged in either
             liquid oxygen or argon.  Liquid argon  is highly recommended
             for use because of the safety hazard associated with liquid

-------
                                 T03-2

             oxygen.  With the sampling valve in the fill  position an
             air sample is then admitted into the trap by  a volume
             .measuring apparatus.   In the meantime,  the column oven is
             cooled to a sub-ambient temperature (-50°C).   Once sample
             collection is completed, the valve  is  switched so that the
             carrier gas sweeps the  contents  of  the  trap onto  the  head of
             the cooled GC column.   Simultaneously,  the liquid cryogen is
             removed and the  trap  is heated to assist  the  sample transfer
             process.   The GC column is  temperature  programmed and  the
             component  peaks  eluting from the columns  are  identified  and
             quantified using flame  ionization and/or  electron  capture
             detection.  Alternate detectors  (e.g. photoionization) can be
             used as appropriate.  An automated  system  incorporating
             these  various operations as well  as the data processing
             function has  been  described  in the  literature  (8,9).
      3.2    Due to the  complexity of ambient air samples,  high resolution
             (capillary  column) GC techniques  are recommended.   However,
            when highly selective detectors (such as the electron
            capture detector) are employed, packed column  technology
            without cryogenic temperature programming can  be effectively
            utilized in some  cases.

4.    Significance

      4.1    Volatile organic  compounds  are emitted  into the atmosphere
            from a  variety of sources including  industrial  and commercial
            facilities, hazardous  waste  storage  facilities,  etc.   Many
            of these compounds are toxic,  hence  knowledge  of the levels
            of such materials in the ambient  atmosphere is  required in
            order  to  determine human health impacts.
      4.2    Because these  organic  species  are present  at ppb levels or
            below,  some means of sample  preconcentration is  necessary  in
            order to acquire  sufficient  material for identification and
            quantisation.  The  two primary preconcentration  techniques
            are  cryogenic  collection  and  the use of solid adsorbents.
            The method  described herein  involves the former technique.

-------
                               T03-3
5.     Definitions

      Definitions used in this document and any user prepared SOPs  should
      be consistent with ASTM D1356 (6).  All  abbreviations and symbols
      are defined within this document at the  point of use.

6.    Interferences/Limitations

      6.1   Compounds having similar GC retention times will interfere
            in the method.  Replacing the flame ionization detector
            with more selective detection systems will help to minimize
            these interferences.  Chlorinated species, in particular,
            should be determined using  the electron capture detector
            to avoid  interference from  volatile hydrocarbons.
      6.2   An important  limitation of  the technique  is the condensation
            of moisture  in  the  collection  trap.  The  possibility of
            ice  plugging  the  trap and stopping the flow is of concern,
            and  water subsequently  transferred to  the capillary column
            may  also  result in  flow stoppage  and cause deleterious effects
            to certain  column materials.   Use of permaselective Nafion®
            tubing  in-line  before  the cryogenic trap  avoids  this problem;
            however,  the material  must  be used with  caution  because  of
            possible  loses  of certain compounds. Another  potential
            problem is  contamination  from the Nafion  ® tubing.  The
             user should consult the literature (7-12) for details on  the
             use  of permeation-type driers.

 7.    Apparatus

       7.1   Gas  chromatograph/Flame lonization/Electron Capture
             Detection System-  must be  capable of  subambient temperature
             programming.  A recent publication (8) describes an automated
             GC  system in which the cyrogenic sampling and analysis
             features are combined.  This system allows simultaneous
             flame ionization and electron capture detection.

-------
                                 T03-4

       7.2   Six-port sampling valve - modified to accept a sample
             collection trap (Figure 1).
       7.3   Collection trap - 20 cm x 0.2 cm I.D. stainless steel
             tubing packed with 60/80 mesh silanized glass beads and sealed
             with glass wool.  For the manual system (Section 9.2) the
             trap is externally wrapped with 28 gauge (duplex and
             fiberglass insulated) type "K" thermocouple wire.   This
             wire, beaded at one end, is connected to a  powerstat
             during the heating cycle.   A thermocouple is also  attached
             to the trap as shown in Figure 1.
       7.4   Powerstat - for heating trap.
       7.5   Temperature readout device - for measuring  trap temperature
             during heating cycle.
       7.6   Glass dewar flask  -  for holding  cryogen.
       7.7   Sample volume  measuring apparatus  - capable  of  accurately
             and  precisely  measuring a  total  sample  volume up to  500 cc
             at sampling rates  between  10 and 200  cc/minute.  See  Section 9.
       7.8   Stopwatch.
       7.9   Dilution  container  for  standards preparation -  glass  flasks
             or Teflon  (Tedlar) bags, .002  inch film thickness  (see
             Figure  2).
       7.10   Liquid  microliter syringes - 5-50 yl  for injecting liquid
             standards into dilution  container.
       7.11   Volumetric  flasks - various  sizes, 1-10 ml.
       7.12   GC column - Hewlett Packard  50 meter methyl silicone cross-
             linked  fused silica column (.3 mm I.D., thick film) or
             equivalent.
       7.13   Mass flow controller - 10-200 mL/minute flow control range.
       7.14   Permeation drier - PermaPure*  - Model MD-125F, or equivalent.
            Alternate designs described in the literature (7-12)  may also
            be acceptable.

8.    Reagents and Materials

      8.1    Glass beads - 60/80 mesh, silanized.

-------
                               T03-5
     8.2   Glasswool  - silanized.
     8.3   Helium - zero grade compressed gas,  99.9999%.
     8.4   Hydrogen - zero grade compressed gas, 99.9999%.
     8.5   Air - zero grade compressed gas.
     8.6   Liquid argon (or liquid oxygen).
     8.7   Liquid nitrogen.
     8.8   SRM 1805 - benzene in nitrogen standard.  Available from the
           National Bureau of Standards.  Additional such standards will
           become available in the future.
     8.9   Chemical standards - neat compounds of interest, highest
           purity available.

9.    Sampling and Analysis Apparatus

      Two systems are described below  which allow collection of an
      accurately known volume of air (100-1000  ml) onto a cryogenically
      cooled trap.  The first system (Section 9.1) is an automated
      device described in the literature (8,9).  The second system
      (Section 9.2) is a manual device, also described in the liter-
      ature  (2).

      9.1    The  automated  sampling and  analysis system is shown in Figure
             3.   This  system is composed of an  automated  GC  system
             (Hewlett  Packard  Model  5880A,  Level 4,  or  equivalent) and  a
             sample collection system  (Nutech Model  320-01,  or  equivalent).
             The  overall  system is  described  in the  literature  (8).

             9.1.1    The electronic console of  the sampling  unit controls
                     the mechanical operation of the six-port valve  and
                     cryogenic trapping components as well  as the tempera-
                     tures in each of  the three zones (sample trap,  transfer
                     line, and valve).

-------
                           T03-6
       9.1.2   The valve (six-port air activated, Seiscor Model 8
               or equivalent) and transfer line are constantly
               maintained at 120°C.   During sample collection the
               trap temperature is maintained at -160 + 5°C by
               a flow of liquid nitrogen controlled by a solenoid
               valve.   A cylindrical  250 with heater, held in
               direct  contact with the trap,  is used to heat the
               trap to 120°C in 60 seconds or less during the sample
               desorption step.   The  construction  of the sample
               trap is described in Section 7.3.
       9.1.3   The  sample flow is  controlled  by a  pump/mass  flow
               controller assembly, as  shown  in Figure  3.  A sample
               flow of 10-100 mL/minute  is generally employed,
               depending  on  the  desired  sampling period.  A  total
               volume  of  100-1000 ml  is  commonly collected.
       9.1.4   In many situations a permaselective  drier (e.g.
               Nafion®) may be required  to remove moisture from
               the  sample.  Such a device  is  installed  at the sample
               inlet.   Two configurations for such devices are
               available.  The first  configuration is the tube and
               shell type in which the sample flow tube  is surrounded
               by an outer shell through which a countercurrent flow
               of clean, dry air is maintained.  The dry air stream
               must be  free from contaminants  and its flow rate should
               be 3-4  times greater than the sample flow to achieve
               effective drying.  A second configuration (7)
               involves placing a drying agent, e.g. magnesium
               carbonate, on the outside of the sample flow tube.
              This approach eliminates the need for a source
              of clean air in the field.  However, contamination
              from the drying agent can be a  problem.

9.2   The manual  sampling consists  of the sample volume measuring
      apparatus shown  in Figure 4  connected to the cryogenic trap/
      GC assembly shown in Figure  1.   The operation of this

-------
                    T03-7

assembly is described below.

9.2.1   Pump-Down Position

        The purpose of the pump-down mode of operation is to
        evacuate the ballast tank in preparation for col-
        lecting a sample as illustrated in Figure 4.  (While in
        this position, helium can also be utilized to back-
        flush the sample line, trap, etc.  However,  this
        cleaning procedure is not normally needed during  most
        sampling operations).  The pump used for evacuating
        the system should be capable of attaining 200 torr
        pressure.

9.2.2   Volume Measuring Position

        Once the system has been sufficiently evacuated,
        the 4-way ball valve is switched to prepare for sample
        collection.  The 3-position valve is used to initiate
        sample flow while the needle valve controls the rate
        of flow.

9.2.3   Sample Volume Calculation

        The volume of air that has  passed through the col-
        lection  trap corresponds to a  known change  in pressure
        within the ballast tank  (as measured by  the Wallace
        Tiernan  gauge).   Knowing the volume, pressure change,
        and temperature  of the system,  the  ideal  gas  law  can
        be  used  to calculate  the number of  moles  of air
        sampled.   On  a  volume basis, this converts  to the
        following  equation:
                       760    TA+  273

-------
                               T03-8

                    where

                         Vs = Volume sampled at 760 mm Hg pressure and
                              25°C.
                         AP = Change in pressure within the ballast tank,
                              mm of Hg.
                         V  = Volume of ballast tank and gauge.
                         TA = Temperature of ballast tank, °C.

                    The internal  volume of the ballast tank and  gauge
                    can be determined either by H20 displacement or by
                    injecting calibrated volumes of air into the system
                    using large  volume  syringes, etc.

10.   Sampling and Analysis Procedure - Manual  Device

      10.1   This  procedure  assumes  the  use  of the  manual  sampling system
            described  in  Section  9.2
      10.2   Prior to sample collection,  the  entire  assembly  should
            be leak-checked.   This  task  is  accomplished by sealing
            the sampling  inlet line,  pumping  the unit  down and placing
            the unit in the flow  measuring mode  of  operation.  An initial
            reading on  the  absolute pressure  gauge  is  taken  and  rechecked
            after 10 minutes.  No apparent change should be  detected.
      10.3   Preparation for sample collection is carried out by  switching
            the 6-port valve to the "fill" position and connecting the
            heated sample line to the sample  source.  Meanwhile  the
            collection trap  is heated to 150°C (or other appropriate
            temperature).  The volume measuring apparatus is pumped-down
            and switched to the flow measuring mode.  The 3-position
            valve is opened and a known volume of sample is then  passed
            through the heated sample line.and trap to putge the
            system.

-------
                               T03-9
     10.4  After the system purge is completed, the 3-position valve is
           closed and the corresponding gauge pressure is recorded.
           The collection trap is then immersed into a dewar of liquid
           argon (or liquid oxygen) and the 3-position valve is
           temporarily opened to draw in a known volume of air, i.e.
           a change in pressure corresponds to a specific volume of
           air (see Section 9).  Liquid nitrogen cannot be used as the
           cryogen since it will also condense oxygen from the air.
           Liquid oxygen represents a potential fire hazard and should
           not be employed unless absolutely necessary.
      10.5  After sample collection  is completed, the 6-port valve is
           switched to the inject position, the dewar is removed and
           the trap is heated  to 150°C to transfer the sample components
           to the head of  the  GC column which  is initially maintained
           at -50°C.  Temperature programming  is initiated to elute
           the compounds of  interest.
      10.6  A GC  integrator  (or data system if  available) is activated
           during the injection  cycle to  provide component identification
           and quantitation.

11.    Sampling and Analysis Procedure  - Automated Device

      11.1  This  procedure  assumes  the use of the automated  system shown
            in  Figure 3.  The components of this system are  discussed
            in  Section  9.1.
      11.2  Prior to initial  sample collection the  entire assembly should
            be  leak-checked.   This  task  is completed by sealing the
            sample inlet line and  noting  that the flow indication or the
            mass flow controller drops to  zero (less than 1  mL/minute).
      11.3  The sample trap, valve, and transfer line are heated to
            120°C and ambient air is drawn through  the apparatus
            (^60 mL/minute) for a period of time 5-10 minutes to flush
            the system, with the sample valve in the inject position.
            During this time the GC column is maintained at 150°C to
            condition  the column.

-------
                                 T03-10
        11.4  The  sample trap is then cooled to -160 + 5°C using a
             controlled flow of liquid nitrogen.  Once the trap
             temperature has stabilized,sample flow through the
             trap is initiated by placing the valve in the inject
             position and the desired volume of air is collected.
       11.5  During the sample collection period the GC column is
             stabilized at -50°C to allow for immediate injection
             of the sample after collection.
       11.6  At the end of the  collection period the valve is
             immediately placed in the  inject  position,  and  the
             cryogenic  trap is  rapidly  heated  to 120°C  to  desorb
             the components onto GC  column.  The  GC  temperature
             program and data acquisition  are  initiated  at this
             time.
       11.7   At the  desired  time the cryogenic  trap is cooled to  -  160'C,
            the valve is returned to the  collect position  and  the  next '
            sample collection  is initiated (to coincide  with the  completion
            of the GC analysis  of the previous sample).

12.    Calibration Procedure

      Prior  to  sample analysis,  and  approximately every  4-6  hours  there-
      after,  a  calibration  standard  must  be analyzed, using  the identical
      procedure employed for ambient air  samples  (either Section 10 or 11).
      This section describes three alternative approaches for  preparing
      suitable  standards.

      12.1  Teflon®  (on Tedlar®)  Bags

           12.1.1   The bag  (nominal size; 20L) is filled with zero air
                    and leaked checked.   This  can be easily accomplished
                    by placing a moderate weight  (text book) on the
                    inflated bag and leaving overnight.   No visible change
                    in bag volume indicates a good seal.   The bag should
                   also be equipped with a quick-connect fitting for
                   sample withdrawal and an insertion port for liquid
                   injections  (Figure 2).

-------
                         T03-11

     12.1.2  Before preparing  a  standard mixture,  the  bag  is
             sequentially filled and evacuated with zero air
             (5 times).   After the  5th  filling,  a  sample blank
             is obtained using the  sampling  procedure  outlined
             in Section  10.
     12.1.3  In order to prepare a  standard  mixture, the bag  is
             filled with a known volume of zero  air.   This flow
             should be measured via a  calibrated mass  flow
             controller or equivalent  flow measuring device.
             A measured aliquot of  each analyte  of interest is
             injected into the bag  through the  insertion port
             using a microliter syringe.   For those compounds
             with vapor pressures lower than benzene or for strongly
             adsorbed species, the  bag  should be heated
             (60°C) oven) during the entire  calibration period.
     12.1.4  To withdraw a sample for analysis,  the sampling line
             is directly connected  to the bag.   Quick  connect
             fittings allow this hook-up to  be  easily  accomplished
             and also minimizes bag contamination  from labora-
             tory air.  Sample .collection is initiated as  described
             earlier.

12.2  Glass Flasks

      12.2.1   If a glass flask is employed  (Figure 2)   the exact
              volume is  determined  by  weighing the flask before
              and after filling with deionized water.   The flask
              is dried by heating at 200°C.
      12.2.2  To prepare a standard, the dried flask is flushed with
              zero air until  cleaned (i.e. a blank run is  made).
              An appropriate aliquot of each analyte  is injected
              using the same procedures as described  for preparing
              bag standards.
      12.2.3  To withdraw a standard for analysis,  the  GC
              sampling line is directly connected  to  the flask
              and a sample obtained.  However,  because the flask

-------
                         T03-12

              is a rigid container, it will not remain at
              atmospheric pressure after sampling has commenced.
              In order to prevent room air leakage into the flask,
              it is recommended that no more than 10% of the initial
              volume be exhausted during the calibration period
              (i.e. 200 cc if a 2 liter flask is  used).

12.3  Pressurized Gas Cylinders

      12.3.1   Pressurized gas cylinders containing selected  analytes
              at ppb concentrations  in  air can  be prepared or
              purchased.   A  limited  number of analytes (e.g.
              benzene,  propane)  are  available from NBS.
      12.3.2   Speciality  gas  suppliers  will  prepare custom gas
              mixtures, and will  cross  reference  the  analyte
              concentrations  to  an NBS  standard for an additional
              charge.   In  general, the  user  should purchase such
              custom  mixtures,  rather than attempting to prepare
              them  because of the special  high pressure filling
             apparatus required. However, the concentrations should
             be checked, either by the supplier or the user using
              NBS reference materials.
     12.3.3  Generally, aluminum cylinders are suitable since most
             analytes of potential interest in this method have
             been shown to be stable for at least several  months
             in such cylinders.  Regulators constructed of stainless
             steel and Teflon®  (no silicon or neoprene rubber).
     12.3.4  Before use the tank regulator should be flushed by
             alternately pressuring with the tank mixture,  closing
             the tank valve, and venting the regulator contents to
             the atmosphere several  times.
     12.3.5  For calibration a continuous flow  of the gas  mixture
             should be maintained through a glass or Teflon® manifold
             from which the calibration standard  is drawn.   To
             generate various calibration concentrations the

-------
                              T03-13
                   pressurized gas mixture can be diluted, as desired,
                   with  zero grade air using a dynamic dilution system
                    (e.g.  CSI Model 1700  ).

13.   Calibration Strategy

      13 1  Vapor phase standards can be  prepared with either neat
            liquids or diluted liquid mixtures  depending  upon the
            concentration levels desired.  It is recommended that  benze'ne,
            also be included in this preparation scheme so that flame
            ionization detector response factors, relative to benzene,
            can  be determined for the other compounds.  The benzene
            concentration generated  in this fashion should be cross-
            checked with  an NBS  (e.g. SRM 1805)  for accuracy determina-
            tions.
       13 2 Under normal  conditions, weekly multipoint calibrations
             should be conducted.   Each multipoint calibration  should
             include a blank  run and  four concentration levels  for the
             target species.   The generated  concentrations should  bracket
             the expected concentration of ambient air samples.
       13  3  A plot of nanograms injected versus area using a linear
             least squares fit of the calibration data will yield  the
             following equation:
                                Y = A + BX

              where
                                 Y = quantity of component,  nanograms
                                 A = intercept
                                 B = slope (response factor)

              If substantial nonlinearity is present in the calibration
              curve a quadratic fit of the data can be used:

-------
                              T03-14

                           Y = A + BX + CX2
            where
                           C = constant


            Alternatively,  a,  stepwise  multilevel  calibration  scheme
            may be used if  more  convenient  for  the  data  system in  use.


14.   Performance Criteria  and Quality  Assurance

      This section summarizes  the quality assurance (QA)  measures  and
      provides guidance concerning performance  criteria  which  should be
      achieved within  each  laboratory.

      14.1   Standard Operating Procedures (SOPs)

            14.1.1  Each user should generate SOPs  describing  the
                   following activities as accomplished  in their
                   laboratories:

                   1)   assembly, calibration and operation of
                        the sampling system.
                   2)   preparation and handling of calibration
                        standards.
                   3)   assembly, calibration and operation of the
                        GC/FID system and
                   4)   all aspects of data recording and processing.

-------
                         T03-15
     14.1.2  SOPs should provide specific stepwise instructions
             and should be readily available to, and understood
             by, the laboratory personnel conducting the work.


14.2  Method Sensitivity, Precision  and Accuracy

      14.2.1  System sensitivity (detection  limit) for each
              component is calculated from the data obtained for
              calibration standards.  The detection limit is
              defined as

                          DL = A + 3.3S

              where

                          DL =  calculated detection limit in
                                nanograms  injected.
                          A  =  intercept calculated in Section 13.
                          S  =  standard deviation of  replicate
                                determination  of the lowest  level
                                standard (at least three  deter-
                                minations are  required).

               For many compounds detection  limits of  1  to 5
               nanograms are found using the flame ionization
               detection.  Lower detection limits can  be obtained
               for chlorinated hydrocarbons using the electron
               capture detector.
        14.2.2  A precision of + 5%  (relative standard deviation)
               can be readily achieved  at concentrations 10
               times the  detection  limit.   Typical performance
               data are  included  in  Table 1.
        14.2.3  Method accuracy  is estimated to  be within +  10%,
               based on  National  Bureau of  Standard calibrated
               mixtures.

-------
                              T03-16


                            REFERENCES
   K   »nidcen^M^ Spi?er,' C" St1cksel, P., Nepsund, K., Ward, G.,
       G flQ offil Lll « K    Tm^l Am An +• i ^ 4 M«	I II „ _ ^   •    »..  .
                                       Analysis oHydcar on
                        «p6nn and,,a?d J1n?1n"«« "81 Ozone  Monitoring
                H™ i   o  ?01^  U:S' Env1ro™ental Protection Agency!
               Triangle  Park, North  Carolina,1982.
  2'   Ani!i!!!r?'J'* Rasm""en' R"  and Holdren, M., "Gas Chromatographic
       ^i^,^rph.^r.:oUifcthr^:ir5i.^?9?rcai'y
  3.   J-onneman, H.  A.,  "Ozone and Hydrocarbon Measurements in Recent
       UX1Q3 Fl L  ll^fln^nftyt ^tiiHTQc"  •?  T *•  r*  ^
       Pollutant and Its Control ProceedingsrEPA-eOO/^-OOla!1!^?3^
  4.   Singh, H., "Guidance for the Collection and Use  of Ambient
       !5e^s D.a.ta.  ^ Development of Ozone Control Strategies",
                                Protection Agency,


  5.    Rlaaln. R.  M  , "Technical Assistance Document for Sampling and
              ironl^l P^?l^-°mP;UndS innAmbl'ent Air", EPA-600/4-83-027.
  6.   Annual  Book of ASTM Standards,  Part 11.03,  "Atmospheric Analysis"
      American  Society for Testing and Materials, Philadelphia  Pen'nsyl'vania,


  7.   Foulger,  B. £.  and  P. G. Sinamouds, "Drier for Field Use in th»
      Determination  of Trace Atmospheric Gases", Anal  Cnem !^ ^9-1090,
                   ion , Anal. Chem., submitted, 1984.
 9.
10'   r°^nT-  M;' S'.Rust»  R- Smith,  and J. Koetz,  "Evaluation of
              iI-'TOt'n* ?TS f?r Collect^9 Organic Conoids in
            Air , Draft Final Report on Contract No. 68-02-3487, 1984.

-------
                              T03-17

                       REFERENCES  (Continued)
11     Cox R.  D.  and  R.  E.  Earp,"Determination of Trace Level Organlcs
      in Ambient Air by High-Resolution Gas c5romat;?raP^£L»
      Simultaneous Photoionization  and Flame  lomzation Detection  ,
      Anal. Chem. 54, 2265-2270,  1982.

12    Burns W  F., 0. T. Tingy,  R.  C. Evans and E.  H. Bates,
      "Problems with a HafloS Membrane Dryer for  Chromatographic
      Samples", J. Chrom.  269. 1-9, 1983.

-------
                               T03-18
 Sample Voluma
 Measuring Apparatus
       G.C. Carrier
       Gas
        Variac
      Temperature
       Controller
  Haatad Sample Line
                    Sample Source
                                a. Fill Position
Sample Voluma
Measuring Apparatus
      G.C. Carrier
      Gas
       Variac
    Temperature
     Controller
Heated Sample Line
                * Sample Source
                                              —	——«^ G.C. Column
                             b.  Injection Position
   Figure 1.   Schematic of Six-Port  Valve Used for Sample
                Collection.

-------
                            T03-19
                                           Septum Seal
               Claw/Teflon V«l»«
Pinhola Insertion^
Port or Septum   \
Injection Port
 20 Liter
Teflon Bag
                                                           \
Quick Connect
Sampling Port
     Figure  2.   Dilution Containers for Standard  Mixtures

-------
     Cryogenic
     Sampling
     Electronics
      Console
 Voltage to Solenoid
Liquid N2
         Solenoid
           Valve
                       Voltage to
                       Cartridge
                        Heaters
                         ill
                                                         Gas Chromatographic System
CD
CO
 i
ro
o
                              FIGURE 3. AUTOMATED SAMPLING AND ANALYSIS
                                         SYSTEM FOR CRYOGENIC TRAPPING

-------
                           T03-21
                      Pump
                                          Vant
                                                               Shut Off Valva
                                                                   Halium Tank
     Ballast Tank
^} Needle Val<

  j     ^^- 3 Position Valvt
                              w
               (1) Gas Chromatograph G-Port Valve
               (2) (Optional 2nd GC System)
               (3) Off
                               1   2
                     (a)  Volumt Measuring Position
                       Pump.
                                              Vent
                                            4 Way Ball Valve        . Shut Off Valve
                                                            u—
                                       Helium Tank
         Ballast Tank
                                 (~\ Needle Valve

                                              3 Position Valve
                                                 (1 > Gas Chromatograph 6-Port Valve
                                                 (2) (Optional 2nd GC System)
                                                 (3) Off
                                 1   2
                        (b) Pump - Down Position

Figure 4.   Sample  Volume  Measuring Apparatus

-------
                TABLE
WHICH
                                                                    CRYOGENIC SAHPLING

Compound
Vinylidene Chloride
Chloroform
1,2-Dichloroethane
Methyl chloroform
Benzene
Trichloroethylene
Tetrachloroethylene
Chlorobenzene

Retention Time,
Minutes'b)
9.26
12.16
12.80
13.00
13.41
14.48
17.37
18.09
Test 1
(4 runs, 200cc
Mean
(Ppb)
144
84
44
63
93
84
69
46

samples)
%RSD
4.4
3.8
3.7
4.5
4.0
3.7
3.7
3.3
Test 2
(8 runs, 200-cc
Mean
(ppb)
6.1
3.5
1.9
2.7
3.9
3.5
2.9
1.9

samples)
%RSD
3.9
5.8
5.1
4.9
5.1
4.1
4.3
3.2
b)GC conditions as follows:
                                                                                     (5cc)
          Column - Hewlett Packard, crosslinked methyl silicone, 0.32 mm ID x 50 m long, thick
                   i i i HI y I U*>6Q 5111 CQ •


          Temperature  Program - 50°C for 2 minutes, then increased at 8°C/minute to 150°C.
                                                                                                             I
                                                                                                            ho
                                                                                                            r-o

-------
                               METHOD T04               Revision 1.0
                                                        April, 1984
        METHOD FOR THE  DETERMINATION  OF  ORGANOCHLORINE  PESTICIDES
              AND POLYCHLORINATED BIPHENYLS  IN  AMBIENT AIR
1.      Scope

       1.1   This document describes a method for determination of a
             variety of organochlorine pesticides and polychlorinated
             biphenyls (PCBs) in ambient air.  Generally, detection
             limits of >1 ng/m3 are achievable using a 24-hour sampling
             period.
       1.2   Specific compounds for which the method has been employed
             are listed in Table 1.  Several references are available
             which  provide further details on the development and
             application of  the method.  The sample cleanup and analysis
             methods  are identical to  those  described in U. S. EPA Method
             608.   That method  is  included as Appendix A of this methods
             compendium.

 2.      Applicable  Documents

        2.1   ASTM  Standards
                 D1356 Definition  of Terms  Related to
                 Atmospheric  Sampling and Analysis (7).
        2.2   Other Documents
                 Ambient Air Studies (1-3)
                 U. S. EPA Technical  Assistance Document (4).
                 U. S. EPA Method 608 (5).   See Appendix A of methods
                 compendium.

 3.     Summary of  Method

        3.1   A modified high volume sampler consisting of a glass
              fiber filter with a  polyurethane foam  (PUF) backup
              absorbent cartridge  is used to sample ambient air at
              a  rate  of ^200-280 L/minute.

-------
                                   T04-2
          3.2   The  filter  and  PUF  cartridge  are  placed  in  clean,  sealed
                containers  and  returned  to  the  laboratory for analysis.
                The  PCBs and pesticides  are recovered by Soxhlet extraction
                with  5% ether in hexane.
          3.3    The extracts are reduced in volume using Kuderna-Danish (K-D)
                concentration techniques and subjected to column chroma-
                tographic cleanup.
          3.4    The extracts are analyzed for pesticides and PCBs using gas
                chromatography with electron capture detection (GC-ECD), as
               described in U.  S.  EPA Method 608 (5).

  4.      Significance

         4.1   Pesticides,  particularly organochlorine pesticides, are widely
              used in both rural and  urban areas for a variety of applications
              PCBs are less widely used, due to extensive restrictions placed
              on their manufacture.   However,  human exposure to PCBs
              continues to be a problem because of their presence in
              various electrical products.
        4.2   Many pesticides and  PCBs exhibit  bioaccumulative,  chronic health
              effects and  hence monitoring  ambient  air  for  such  compounds
              is of  great  importance.
        4.3   The relatively  low levels of such compounds in the environment
              requires  the  use  of high volume sampling techniques  to
              acquire sufficient sample for analysis.  However, the volatility
              of these compounds prevents efficient collection on  filter
              media.  Consequently, this method utilizes both a filter and
              a  PUF backup cartridge which provides for efficient collection
              of most organochlorine pesticides, PCBs, and many other organics
             within the same volatility range.

5.     Definitions

             Definitions used in this  document  and  any  user-prepared  SOPs
             should  be consistent with ASTM D1356 (7).  All  abbreviations

-------
                               T04-3

             and symbols are defined  within this  document  at  the  point  of
             use.
6.     Interferences
       6.1   The use of column chromatographic cleanup and selective GC
             detection (GC-ECD) minimizes the risk of interference from
             extraneous organic compounds.  However, the fact that PCBs
             as well as certain organochlorine pesticides (e.g. toxaphenfe
             and chlordane) are complex mixtures of individual compounds
             can cause difficulty in accurately quantifying a particular
             formulation in a multiple component mixture.
       6.2   Contamination of glassware and sampling apparatus with traces
             of pesticides or PCBs can be a major source of error in the
             method, particularly when sampling near high level sources
              (e.g.  dumpsites, waste processing plants, etc.) careful attention
              to cleaning and  handling procedures  is required  in all steps
              of the sampling  and analysis to  minimize  this  source of error.
 7.      Apparatus
        7.1   Hi-Vol  Sampler with PUF cartridge - available from General
              Metal Works (Model  PS-1).   See Figure 1.
        7.2   Sampling Head to contain glass cartridge with PUF  plug - available
              from General Metal  Works.   See Figure 2.
        7.3   Calibration orifice - available from General Metal Works.
        7.4   Manometer - to use with calibration orifice.
        7.5   Soxhlet extraction system - including Soxhlet extractors
              (500 and 250 ml), heating mantels, variable voltage trans-
              formers, and cooling water source - for extraction of PUF
              cartridges  before and after sampling.  Also for extraction of
              filter samples.
        7.6   Vacuum oven connected to water aspirator -  for drying
              extracted  PUF  cartridges.
        7.7   Gas  chromatograph with electron  capture detector  -  (consult
              U. S.  EPA  Method 608  for specifications).

-------
                                 T04-4

        7.8    Forceps  -  to  handle quartz fiber filter samples.
        7.9    Die  -  to cut  PUF  plugs..
        7.10   Various  items  for extract preparation, cleanup, and analysis
              consult  U. S.  EPA Method 608 for detailed listing.
        7.11   Chromatography column - 2 mm I.D. x 15 cm long - for alumina
              cleanup.

8.      Reagent and  Materials

        8.1    Polyurethane foam - 3 inch thick sheet stock, polyether
              type used  in furniture upholstering.  Density 0.022 g/cm3.
        8.2    Polyester  gloves -  for handling PUF cartridges and filters
        8.3    Filters, quartz fiber - Pallflex 2500 QAST , or equivalent.

        8.4    Wool felt  filter - 4.9 mg/cm2 and 0.6 mm thick.  To fit
              sample head for collection efficiency studies.  Pre-
              extracted with 5% diethyl  ether in hexane.
        8.5    Hexane - Pesticide or distilled in glass grade.
        8.6    Diethyl ether - preserved with 2% ethanol  -  distilled in
              glass grade,  or equivalent.
        8.7   Acetone - Pesticide or distilled in glass  grade.
        8.8   Glass container for PUF cartridges.
        8.9   Glass petri dish - for shipment of filters to and from the
              laboratory.
        8.10   Ice chest - to store samples at ^0°C after collection.
        8.11   Various materials needed for extract preparation; cleanup,
             and analysis  - consult U.  S.  EPA Method 608  for details
              (Appendix A of this compendium).
       8.12  Alumina - activity grade IV.  100/200 mesh

9.     Assembly and Calibration of Sampling  Apparatus

       9.1   Description of Sampling Apparatus
             9.1.1   The entire sampling  system is  diagrammed in Figure 1.
                     This  sampler was developed by  Syracuse University

-------
                       T04-5

              Research  Corporation  (SURC) under a  U. S.  EPA
              contract  (6)  and  further modified by Southwest
              Research  Institute  and  the U.  S. EPA.  A  unit
              specifically  designed for this method  is  now commer-
              cially available  (Model PS-1  - General Metal Works,
              Inc.,  Village of  Cleves, Ohio).  The method
              writeup assumes the use of the commercial  device,
              although  the  earlier modified device is also con-
              sidered acceptable.
      9.1.2   The sampling  module (Figure 2) consists of a glass
              sampling  cartridge  and  an air-tight  metal  cartridge
              holder.  The  PDF  plug is retained  in the  glass
              sampling  cartridge.

9.2   Calibration of Sampling  System

      9.2.1   The airflow through the sampling system  is monitored
              by a venturi/Manehelic assembly, as  shown in  Figure  1.
              A  multipoint calibration of  the venturi/mag-
              nehelic assembly must be  conducted every  six  months
              using an  audit calibration  orifice,  as described in
              the U. S. EPA High Volume  Sampling Method (8).   A
              single point calibration  must be performed before
              and after each sample collection,  using  the  procedure
              described below.
      9.2.2   Prior to calibration a "dummy" PUF cartridge  and
              filter are placed  in the sampling head and the sampling
               motor is activated.  The flow control valve is
              fully opened and the voltage  variator is  adjusted
               so that  a  sample flow  rate corresponding to ^110% of
              the desired  flow rate  is indicated  on the magnehelic
               (based on the previously obtained multipoint cali-
              bration  curve).  The motor is allowed to warmup
              for ^10  minutes  and  then the  flow control valve is
              adjusted to  achieve  the desired flow  rate.  The
              ambient  temperature  and barometric  pres:jre s ould

-------
                                 T04-6

                      be recorded on an appropriate data sheet (e.g.  Figure 3),
              9.2.3   The calibration orifice is then placed on the sampling
                      head and a manometer is attached to the tap on  the
                      calibration orifice.  The sampler is momentarily
                      turned off to set the zero level  of the manometer.
                      The sampler is then  switched  on and the manometer
                      reading is recorded, once a stable reading  is
                      achieved.   The sampler is then  shut off.
              9.2.4    The calibration  curve for the orifice  is  used to
                      calculate  sample flow from the  data  obtained in
                      9.2.3,  and the calibration curve  for the  venturi/
                      magnehelic assembly  is  used to  calculate  sample
                      flow from  the  data obtained in  9.2.2.  The  calibra-
                      tion data  should  be  recorded on an appropriate
                      data sheet  (e.g.  Figure 3).  If the two values  do
                      not agree within  10% the  sampler should be  inspected
                      for damage, flow blockage, etc.   If no  obvious problems
                     are found the sampler should be recalibrated (multi-
                     point) according to the U. S.  EPA High Volume
                     Sampling procedure (8).
             9.2.5   A multipoint calibration of the  calibration  orifice,
                     against a primary standard, should be obtained
                     annually.

10.     Preparation of Sampling (PUF) Cartridges

       10.1   The  PUF adsorbent is a polyether-type  polyurethane foam
             (density No. 3014 or 0.0225 g/cm3).  This  type  of foam
             is used for furniture upholstery.   It  is white and yellows
             on exposure to  light.
       10.2   The  PUF inserts  are 6.0 cm diameter cylindrical  plugs cut
             from 3  inch sheet stock and should fit with slight com-
             pression  in the  glass  cartridge, supported  by the  wire

-------
                            T04-7

           screen.   See  Figure  2.   During cutting the die is rotated
           at  high  speed (e.g.  in a drill press) and continuously
           lubricated with  water.
     10.3  For initial cleanup  the  PUT  plug  is  placed in a  Soxhlet
           extractor and extracted  with acetone for  14-24 hours  at
           approximately 4  cycles per hour.   When cartridges are
           reused,  5% diethyl  ether in  n-hexane can  be  used as  the
           cleanup  solvent.
     10.4  The extracted PUF is placed  in  a  vacuum  oven connected
           to a water aspirator and dried  at room  temperature  for
           approximately 2-4 hours  (until  no solvent odor  is detected).
     10.5  The PUF is placed into the glass  sampling cartridge  using
           polyester gloves.  The module is  wrapped with hexane
           rinsed aluminum foil, placed in  a labeled container
           and tightly sealed.
     10.6  Other adsorbents may be suitable for this method as indicated
           in the various  references (1-3).   If such materials are
           employed  the user must  define appropriate preparation
           procedures based on the information contained in these
           references.
     10.7  At least  one assembled  cartridge from each batch must be
           analyzed,  as a  laboratory blank, using the procedures
           described in Section 12,  before  the batch is considered
           acceptable for  field use.   A blank  levelof <10 ng/plug
           for  single compounds is considered  to be acceptable.  For
           multiple  component  mixtures (e.g. Arochlors) the blank level
           should  be <100  ng/plug.

11.    Sampling

      11.1  After the sampling  system has been  assembled and calibrated
           as described in Section 9 it can be used  to collect  air
            samples as described below.
      11.2 The samples should be located  in an unobstructed area, at
            least two meters from any obstacle  to air flow.  The
            exhaust hose should be  stretched out in  the downwind

-------
urao^iAua pun XSoioDa                                          Jeded papAo9J


                          T04-8
      direction to prevent recycling of air.
 11.3 A clean sampling cartridge  and quartz fiber filter are removed
      from sealed transport  containers  and placed in  the sampling
      .head using forceps  and gloved hands.   The  head  is  tightly sealed
      into the sampling system.   The aluminum foil  wrapping  is
      placed back in  the  sealed container for later use.
 11.4 The zero reading of the Magnehelic is checked.   Ambient
      temperature, barometric pressure,  elapsed  time  meter setting,
      sampler serial  number, filter number and PUT cartridge number
      are recorded.   A suitable data sheet is shown in Figure 4.
 11.5 The voltage variator and flow control  valve are placed at the
      settings used in 9.2.3 and  the power switch is  turned  on.
      The elapsed time meter is activated and the start  time recorded.
      The flow (Magnehelic setting)  is  adjusted,  if necessary using
      the flow control  valve.
 11.6 The Magnehelic  reading is recorded every six  hours  during
      the sampling period.   The calibration  curve (Section 9.2.7)  is
      used to calculate the  flow  rate.   Ambient  temperature  and
      barometric  pressure  are  recorded  at the beginning and  end of
      the sampling period.
 11.7 At  the  end  of the desired sampling period  the power is  turned
     off and the filter and PUF  cartridges are wrapped with  the
     original  aluminum foil  and  placed  in  sealed,  labeled containers
     for transport back to  the laboratory.
 11.8 The Magnehelic  calibration  is  checked using the  calibration
     orifice as  described in  Section 9.2.4.   If  the  calibration
     deviates  by more than  10% from the  initial  reading  the  flow  data
     for that  sample must be  marked as  suspect and the sampler
     should  be inspected  and/or  removed  from service.
 11.9 At  least  one field blank will  be returned to  the laboratory
     with each group of samples.   A field blank  is treated exactly
     as  a sample  except that  no  air is drawn  through  the cartridge.

-------
                             T04-9

      11.10  Samples are stored at ^20°C in an ice chest until  receipt at
            the  analytical  laboratory, at which  time they are stored
            refrigerated  at 4°C.

12.   Sample Preparation  and Analysis

      12.1   Sample Preparation

            12.1.1  All  samples should be extracted within  1  week after
                    collection.
            12.1.2  PUF cartridges are removed from the sealed con-
                    container using gloved hands, the aluminum foil
                    wrapping is removed, and the cartridges are placed
                    into a  500-mL Soxhlet extraction.  The cartridges are
                    extracted  for 14-24 hours at ^4 cycles/hour with 5%
                    diethyl  ether in  hexane.  Extracted cartridges can be
                    dried  and  reused  following  the handling procedures
                    in Section 10.  The quartz  filter  can  be placed  in
                    the  extractor with  the  PUF  cartridges.  However, if
                    separate analysis is  desired  then  one  can  proceed  with
                     12.1.3.
             12.1.3  If separate analysis  is desired,  quartz  filters are
                     placed in a 250-mL Soxhlet  extractor and extracted
                     for 14-24 hours with 5% diethyl  ether  in hexane.
             12.1.4  The extracts are concentrated to 10 ml final
                     volume using 500-mL Kuderna-Danish concentrators
                     as described in EPA Method 608 (5), using a hot water
                     bath.  The concentrated extracts are stored refrigerated
                     in  sealed 4-dram vials having teflon-lined screw-caps
                     until  analyzed or subjected to cleanup.

        12.2  Sample Cleanup

              12.2.1   If  only organochlorine pesticides and PCBs  are  sought,
                      an  alumina cleanup procedure  reported in  the  literature
                      is  appropriate (1).   Prior to cleanup the sample

-------
                                  T04-10
                     extract is carefully reduced to 1 ml using a gentle
                     steam of clean nitrogen.
             12.2.2  A glass chromatographic column (2 mm ID x 15 cm long)
                     is packed with alumina, activity grade IV and rinsed
                     with ^20 ml of n-hexane.  The concentrated sample
                     extract (from 12.2.1)  is placed on the column and
                     eluted with 10 ml of n-hexane at a rate of 0.5
                     mL/minute.   The eluate  volume is adjusted  to
                     exactly 10  ml and analyzed  as described in  12.3.
             12.2.3  If other pesticides  are  sought,  alternate  cleanup
                     procedures  (e.g.  Florisil)  may  be  required.  Method
                     608  (5)  identifies appropriate  cleanup  procedures.

       12.3  Sample Analysis

             12.3.1   Sample  analysis  is performed  using 6C/ECD  as
                     described in  EPA  Method  608 (5).  The user must
                     consult  this  method  for  detailed  analytical  procedures.
             12.3.2   GC retention  times and conditions are identified
                     in Table 1 for the compounds of interest.

13.   GC Calibration

      Appropriate calibration procedures are identified in  EPA Method
      608 (5).

14.   Calculations

      14.1   The  total sample volume Ofo )  is  calculated  from  the
            periodic flow readings (Magnehelic)  taken  in Section
            11.6  using  the  following equation.
                                        N      1000

           where

-------
                         T04-11
                                         2
               V   = Total sample volume  (m ).
               Q-i, QO-..QM  =  Flow  rates  determl'ned at the
                   beginning,  end,  and  intermediate points during
                   sampling  (L/minute).
               N  » Number of  data  points averaged.
               T  = Elapsed  sampling  time (minutes).
14.2  The volume  of air sampled can  be converted to  standard
      conditions  (760 mm Hg pressure and 25°C)  using the following
      equation:

                          A       298
               v  =  v  X —  X   **°
                5    m   760    273+tA

      where

               V  = Total  sample  volume at 25°C and 760 mm Hg
                    pressure (m )                                3
               V  = Total  sample  flow under ambient conditions (m )
                m                    /   H \
               P. = Ambient  pressure  (mm Hg)
               t, = Ambient  temperature (°C)
                A

 14.3  The concentration of compound in  the sample is calculated
       using the  following  equation:
                      A x Vc
                CA =
                      V.xvs
       where
                C. « Concentration of analyte in the sample,
                     yg/m
                A  = Calculated amount of material injected onto
                     the chromatograph based on calibration curve
                     for injected standards  (nanograms)
                V. = Volume of extract injected (yL).

-------
                                T04-12

                        VE = Final volume  of  extract  (ml).
                        Vs = Total volume  of air samples corrected to
                             standard conditions (m3).

14.    Performance Criteria and  Quality Assurance

      This  section summarizes the  quality  assurance (QA) measures  and
      provides  guidance  concerning performance criteria which should
      be  achieved  within each laboratory.

      14.1  Standard Operating Procedures  (SOPs)

           14.1.1  Users should generate SOPs describing the follow-
                   ing activities as accomplished in  their laboratory:
                   1)  assembly, calibration and operation  of the
                   sampling system, 2) preparation, purification,  storage
                   and handling of sampling cartridges,  3)  assembly,
                   calibration  and operation  of the GC/ECD  system, and
                   4)  all  aspects  of data  recording and  processing.
           14.1.2   SOPs  should  provide specific  stepwise instructions
                   and should be readily available to, and  understood
                   by, the  laboratory  personnel  conducting  the work.

     14.2   Process, Field, and Solvent Blanks

           14.2.1  One PUF cartridge and filter from each batch of
                  approximately twenty should be analyzed, without
                  shipment to the field, for the compounds of
                  interest to serve as a process blank.
          14.2.2  During each sampling episode at least  one PUF
                  cartridge and filter should be shipped to the field
                  and  returned,  without drawing air through the sampler,
                  to serve as a  field blank.
          14.2.3  During the analysis  of each batch of samples  at
                  least  one  solvent process blank  (all steps conducted
                  but  no PUF cartridge or  filter included)  should  be

-------
                         T04-13

             carried through the procedure and analyzed.
      14.2.4  Blank  levels  should not exceed -v.10 ng/sample for
             single components or ^100 ng/sample for multiple
             component  mixtures  (e.g. PCBs).

14.3  Collection Efficiency and Spike Recovery

      14.3.1   Before using the method for sample  analysis  each
              laboratory must determine  their collection
              efficiency for the  components of interest.
      14.3.2  The glass fiber filter in  the sampler is  replaced
              with a hexane-extracted wool felt filter  (weight
              14.9 mg/cm2, 0.6 mm thick).  The filter is spiked
              with microgram amounts of the compounds of interest
              by dropwise  addition of hexane solutions  of the
              compounds.   The solvent is allowed to evaporate
              and filter  is placed into the sampling system for
              immediate use.
       14.3.3  The sampling system, including a clean PUF  cartridge,
              is activated and set at the  desired  sampling flow
              rate.  The  sample  flow is monitored  for  24  hours.
       14.3.4  The filter  and PUF cartridge are then  removed and
              analyzed  as described  in  Section 12.
       14.3.5  A second  sample, unspiked  is collected over the
               same  time period to  account for any  background
               levels  of components in  the ambient  air  matrix.
       14.3.6  A third PUF cartridge is  spiked with the same  amounts
               of the compounds  used in  14.3. 2 and  extracted  to
               determine analytical recovery.
       14.3.7  In general  analytical  recoveries  and collection
               efficiencies of 75% are considered to be acceptable
               method performance.

-------
                         T04-14

      14.3.8  Replicate (at least triplicate)  determinations  of
              collection efficiency should  be  made.   Relative
              standard deviations for these replicate determinations
              of + 15% or less  is considered acceptable  performance.
      14.3.9  Blind spiked samples should be included with  sample
              sets periodically,  as a check on analytical per-
              formance.

14.4  Method Precision and Accuracy

      Typical method recovery data are shown in Table 1.  Re-
      coveries for the various  chlorobiphenyls illustrate the
      fact that all components  of an Arochlor  mixture will  not
      be retained to the same extent.  Recoveries  for tetrachloro-
      biphenyls and above are generally greater than 85% but
      di- and trichloro homologs  may not be recovered quantitatively.

-------
                       T04-15
                     REFERENCES
   °B»se:rde £»;£&• 'i^™^ «^ AI ,
   Anal. Chem.  49, 1668-1672, 1977.
'
    Park, NC, 1980
    Park, NC, 1983.
5-  assr^u s
    EPA-600/4-82-057! U. S. Environmental Protection Agency,
    Cincinnati, OH, 1982.
 "
    Association, Durham, NC, 1970
 7.


     1983.
 8    Reference Method for the Determination of Suspended Particulates

     in the Atmosphere (High Volume Method). Federal Register,

     Sept. 14, 1972 or 40CFR50 Appendix B.

-------
                                     T04-16
TABLE 1.  SELECTED COMPONENTS DETERMINED USING HI-VOL/PUF SAMPLING PROCEDURE
24-Hour Sampling Efflciency(b)
Compound
Aldrin
4,4'-DDE
4,4'-DDT
Chlordane
Chlorobiphenyls
4,4' Di-
2,4,5 Tri-
2, 4', 5 Tri-
2, 2', 5, 5' Tetra-
2, 2', 4, 5, 5' Penta-
2, 2', 4, 4', 5, 5' Hexa
GC Retention
Time, Minutest3 )
2.4
5.1
9.4
(c)

--
—
—
—
—
--
Air
Concentration
ng/m3
0.3-3.0
0.6-6.0
1.8-18
15-150

2.0-20
0.2-2.0
0.2-2.0
0.2-2.0
0.2-2.0
0.2-2.0
%
Recovery
28
89
83
73

62
36
86
94
92
86
  (a)   Data from U.S. EPA Method 608.  Conditions are as follows;
        Stationary Phase - 1.5% SP2250/1.95% SP-2401 on
        Supelcoport (100/120 mesh) packed in 1.8 mm long x
        4 mm ID glass column.
        Carrier - 5/95 methane/Argon at 60 mL/Minute
        Column Temperature - 160°C except for PCBs  which are
        determined at 200°C.
  (b)   From Reference 2.
  (c)   Multiple component formulation.  See U.S.  EPA Method  608.

-------
                            T04-17
                  Sampling
                   Head
                (See Figure 2)
Magnehelic
  Gauge
 0-100 in.
  Exhaust
   Duct
(6 in. x 10 ft)
                                                     Voltage Variator


                                                     Elapsed Time Meter
       FIGURE 1.  HIGH VOLUME AIR SAMPLER.  AVAILABLE
                 FROM GENERAL METAL WORKS (MODEL PS-1)

-------
Lower Canister
                                                                                         Filter Holder
                                                                                         With Support
                                                                                            Screen
                                                                                               4" Diameter Filter
                                   Glass Cartridge
                                    and Puf Plug
                      Silicone Rubber
                         Gaskets
                                                                   Filter Retaining Ring-
                                                                                                                            -H
                                                                                                                            O
                                                                                                                            -c*
                                                                                                                             I
                                                                                                                            00
Silicone -
Rubber
Gasket
                                   FIGURE 2.  SAMPLING HEAD

-------
  Performed by_
  Date/nine
Calibration Orifice
Manometer S/M	
S/M
 Ambient Teaperature_
Bar.Press. 	
                                                            Hg
Sampler
S/N
















Varlac
Setting V
















Timer OK?
Yes/No
















Calibration Orifice
Data
Manometer,
In. H20
















Flow Rate,
son /min(')
















Sampler
Venturl Data
Magnetic lie,
In. H20
















Flow Rate
scm/mln W
















S Difference Between
Calibration and Sample
Venturl Flow Rates
















Comments
















                                                                                                                                                 o
                                                                                                                                                 -e-
(a)  From Calibration Tables  for Calibration Orifice or Venturl Tube
(b)  From Calibration Tables  for Venturl  Tube  1n each Hi-Vol  unit.
                                    Date check by
                                                                          Date
                                   FIGURE 3.   TYPICAL CALIBRATION  SHEET  FOR HIGH VOLUME SAMPLER

-------
Simirior
S/N
l>) ROHKO-
Sampling Location
ID
MV •vidwie* of Mini
NOT
F«t« lv'
Mrmff wtthM
PUFC.H
No.
Mnplor aml/o
Vcrisc
S*nin«
r •bnormi

Sun. hr CD
Mint in umptor
Cloch Tim*
Slop, hr CD
OCMrition. PU

M« EI.P.M
: onridgt cond

Stin. mm
ition or handlir
S*mpl*t Timar
Step, mm
if, tte.
Min ELpwd

Vcnturi RMdmgr Tim>/M«gn«nlic in. H2
1

2

3

4

Ambi*n1
T«mp«r»tur«. "C
S»n

Stop

B«fomvtric
S»n

Stop





— 1
o
.Cr
1
ro
o
                                     D>» ChKkrd By.
FIGURE 4.    TYPICAL SAMPLING DATA FORM FOR HIGH VOLUME PESTICIDE/PCB SAMPLER

-------
                                 METHOD T05              Revision  1.0
                                                        April, 1984
   METHOD FOR THE DETERMINATION  OF ALDEHYDES AND KETONES  IN AMBIENT  AIR
           USING HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC)

1.      Scope

       1.1   This document describes a method for determination of
             individual aldehydes and ketones in ambient  air.   With
             careful attention to reagent purity and other factors
             the method can detect most monofunctional aldehydes and
             ketones at the 1-2 ppbv level.
       1.2   Specific compounds for which the method has  been employed
             are listed in Table 1.  Several studies have used the
             same basic method, with minor procedural differences,
             for analysis of ambient air (1-3).

 2.     Applicable Documents

       2.1   ASTM Standards:
             D  1356  Definitions of  Terms Related to Atmospheric
             Sampling  and Analysis  (s)

       2.2   Other  Documents
             Ambient air  studies  (1-3).
              U.S. EPA Technical  Assistance  Document  (4)

 3.    Summary  of Method

        3.1    Ambient air  is  drawn through  a midget impinger containing 10 mL
              of 2I\[ HC1/0.05% 2,4-dinitrophenylhydrazine  (DNPH  reagent)
              and 10 mL of isooctane.   Aldehydes and  ketones readily
              form stable  2,4-dinitrophenylhydrazones (DNPH derivatives).

-------
                                  T05-2
        3.2   The  impinger  solution  is  placed  in  a  screw-capped vial having
              a  teflon-lined  cap  and  returned  to  the  laboratory for analysis,
              The  DNPH  derivatives are  recovered  by removing the isooctane
              layer,  extracting the aqueous layer with 10 ml of 70/30
              hexane/methylene chloride, and combining the organic
              layers.
        3.3   The  combined  organic layers  are evaporated to dryness under
              a  steam of  nitrogen and the  residue dissolved in methanol.
        3.4   The  DNPH  derivatives are  determined using reversed phase
              HPLC with an  ultraviolet  (UV) adsorption detector operated
              at 370  nm.

4.      Significance

        4.1    Aldehydes and ketones are emitted into  the atmosphere from
              chemical  operations and various combustion sources.  In
              addition, several of these compounds  (e.g.  formaldehyde and
              acetaldehyde) are produced by photochemical  degradation
              of other organic compounds.  Many of these compounds are
              acutely toxic and/or carcinogenic, thus requiring their
              determination in ambient air in order to assess  human
              health impacts.
       4.2    Conventional methods for aldehydes and ketones have generally
              employed colorimetric techniques wherein only one or two
              compounds are detected, or the sum of numerous compounds
              is determined.  The  method described herein  provides  a
             means for specifically  determining a wide variety of aldehydes
             and ketones  at typical  ambient concentrations.

5.     Definitions

       Definitions used in  this document and  any  user prepared SOPs
       should be consistent with  ASTM D1356(5).   All  abbreviations and
       symbols are defined  within this  document at  the point  of use.

-------
                               T05-3
6.     Interferences
       6 1   The only significant interferences in the method are certain
             isomeric aldehydes or ketones which may be unresolved by
             the HPLC system.  Such interferences can often be overcome by
             altering the separation conditions (e.g.  using alternate
             HPLC columns or mobile phase compositions).
        6.2   Formaldehyde contamination of the  DNPH reagent  is a
             frequently  encountered problem.   The reagent must be
             prepared within 48  hours  before use  and  must  be  stored  in
             an uncontaminated environment  before and after sampling to
             minimize  blank problems.  Acetone contamination  is
              apparently unavoidable.   Consequently,  the method  cannot be
              used to accurately  measure  acetone levels except in highly
              contaminated environments.
 7.     Apparatus
         7  1    Isocratic HPLC system-consisting of high pressure
               pump,  injection valve, Zorbax CDS column (25 cm x 4.6 mm ID),
               variable wavelength  UV detector, and data  system or
               stripchart  recorded.  See  Figure 3.
         7 2   Sampling  system-capable  of accurately  and  precisely
               sampling  100-1000 mL/minute of  ambient air.   See  Figure  1.
         7.3   Stopwatch
         7.4   Friction top metal can e.g.  one-gallon  (paint can) - to hold
               DNPH reagent and samples
         7.5   Thermometer - to record ambient temperature.
         7.6   Barometer  (optional)
         7.7   Analytical balance - 0.1 mg sensitivity
         7.8   Reciprocating shaker
          7.9   Midget impingers  -  jet  inlet type - 25 mL volume.
          7.10  Ice  bath - for cooling  impingers during sampling.

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                                 T05-4

        7.11   Nitrogen evaporator with heating block  -  for concentrating
              samples
        7.12   Suction filtration  apparatus  -  for  filtering HPLC
              mobile  phase.
        7.13   Volumetric  flasks -  100  mL and  500  ml.
        7.14   Pipettes  -  various  sizes, 1-10  ml.
        7.15   Helium  purge line (optional)  -  for  degassing HPLC
              mobile  phase.
        7.16   Erlenmeyer  flask, 1-liter - for preparing HPLC mobile
              phase.
        7.17  Graduated cylinder,  1 liter - for preparing HPLC mobile
             phase.
        7.18  Microliter syringe,  10-25 uL  - for HPLC  injector.

8.     Reagents and Materials

       8.1    Bottles, 10  oz.  glass,  with teflon-lined screw cap  -  for
             storing  DNPH reagent.
       8.2    Vials, 50 mL, with teflon-lined  screw cap  -  for holding
             samples  and  extracts.
       8.3    Disposable pipettes  and bulbs.
       8.4    Granular charcoal.
       8.5    Methanol,  hexane, methylene chloride, isooctane - distilled
             in glass or  pesticide grade.
       8.6    2,4-Dinitrophenylhydrazine - highest purity available
             (20% moisture).
       8.7    Nitrogen, compressed  gas cylinder -99.99%  purity for
             sample evaporation.
      8.8    Polyester filters, 0.22 ym - Nuclepore or equiv.
      8.9   DNPH derivatives of the components of interest -
            synthesized from DNPH and  neat aldehydes  according
            to reference  (7).  Recrystallized from ethanol before
            use.

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                               T05-5

9.     Preparation of DNPH Reagent

       9.1   Each batch of DNPH reagent should be prepared and purified
             within 48 hours of sampling, according to the procedure
             described in this section.
       9.2   Two hundred and fifty milligrams of solid 2,4-dinitro-
             phenylhydrazine and 90 ml of concentrated hydrochloric
             acid are placed into a 500 ml volumetric flask and the
             flask is filled to the mark with reagent water.  The
             flask is then inverted several times or sonified until  all  of
             the solid material has dissolved.
       9.3   Approximately 400 ml of the DNPH reagent is placed in a
             16 ounce glass screw-capped bottle having a teflon-lined
             cap.  Approximately  50 ml of a 70/30  (V/V) hexane/methylene
             chloride mixture  is  added to the bottle and the capped
             bottle  is shaken  for 15 minutes  on a  reciprocating shaker.
             The  organic  layer is then removed and  discarded by decanting
             as much as possible  and using a  disposable pipette to
             remove  the remaining organic layer.
       9.4   The  DNPH reagent  is  extracted two more times  as described
             in  9.3.  The bottle  is then tightly  capped,  sealed with
             teflon  tape, and  placed  in  a friction top can (paint  can)
             containing a 1-2  inch  layer of  granulated charcoal.   The
             bottle  is kept in the  sealed  can prior to use.
        9.5   A portion of the  DNPH  reagent  is analyzed using the
             procedure described  in Section  11  prior to  use in order  to
             ensure  that  adequate background levels are  maintained.

 10.    Sampling

       10.1  The  sampling apparatus is assembled  and should  be similar  to
             that shown in  Figure 1.   EPA Method  6  uses essentially the same
             sampling system (8).  All glassware  (e.g. impingers, sampling
             bottles,  etc.) must  be thoroughly rinsed with methanol and oven
             dried before use.

-------
                         T05-6
   10.2  Prior to sample collection the entire assembly (including
        empty sample impingers) is installed and the flow rate
        checked at a value near the desired rate.  In general
        flow rates of 100-1000 mL/minute are useful.   Flow rates
        greater than *1000 mL/minute should not be used because
        impinger collection efficiency may decrease.   Generally
        calibration is  accomplished using a soap bubble flow
        meter or calibrated wet test  meter connected  to the flow
        exit, assuming  the entire  system  is sealed.   ASTM  Method
        D3686 describes an appropriate  calibration scheme  not
        requiring a  sealed flow system  downstream of  the pump.
  10.3   Ideally  a dry gas  meter is  included  in the system to'record
        total flow.  If a  dry gas meter is  not available the operator
       must  measure and record  the sampling flow rate at the
       beginning and end of the sampling period to determine
       sample volume.   If the sampling period exceeds two hours
       the flow rate should be measured at intermediate points
       during the sampling period.   Ideally a  rotameter should be
       included  to  allow observation  of the flow rate without
       interruption  of  the sampling process.
 10.4   To  collect an air sample two clean midget  impingers are
       loaded with  10 ml of purified  DNPH reagent and 10 mL of
       isooctane.  The  impingers are connected in series to
       the sampling system and  sample flow  is started.  The follow-
       ing parameters are  recorded on the data sheet  (see Figure 3
      for an example):   date, sampling location, time, ambient
      temperature, barometric pressure (if available), relative
      humidity (if available), dry gas meter reading  (if appro-
      priate), flow rate,  rotometer setting, DNPH reagent batch
      number, and dry gas  meter and pump  identification numbers.
10.5  The  sampler is allowed to operate for the  desired period,
      with periodic recording of the  variables  listed above.
      The  total  flow should not exceed  «u80 liters.  The operator
      must ensure  that  at  least 2-3 ml  of isooctane remains in
      the  first  impinger at  the end of  the  sampling interval
      (i.e.  for  high ambient  temperatures  lower  sampling volumes
     may  be  required).

-------
                       T05-7

10.6  At the end of the sampling period the parameters  listed
      in 10.4 are recorded and the sample flow is stopped.   If
      a dry gas meter is not used the flow rate must be checked
      at the end of the sampling interval.  If the flow rate
      at the beginning and end of the sampling period differ
      by more than 15% the sample should be marked as suspect.
10.7  Immediately after sampling the impingers are removed from
      the sampling system.  The contents of the first impinger
      are emptied into a clean 50 ml glass vial having a teflon^
      lined screw cap.  The first impinger is then rinsed with
      the contents of the second (backup) impinger and the rinse
      solution is added to the vial.  The vial is then capped,
      sealed with teflon tape and placed in a friction top can
      containing 1-2 inches of granular charcoal.  The samples
      are stored in the can, refrigerated until analysis.
10.8  If a  dry gas meter or equivalent total flow indicator is
      not used the average sample flow rate must be calculated
      according to the  following equation:

                       Q     Q1 +Q2  •••• QN
                        A            N
      where

      Q. =  Average flow rate  in mL/minute.
      0,,  Q2,...QN=  Flow rates determined  at  the
                      beginning, end,  and  intermediate
                      points  during  sampling.
       N =  Number  of  points averaged.
 10.9   The  total  flow is then  calculated  using  the  following
       equation:
                              (T2-T,)I1A
                       " m ~
                               1000
                       Vm = Total  volume sampled in liters  at  measured
                            temperature and pressure
                       T2  = Stop time
                       T1  » Start time (T2-T] given in minutes)

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                                T05-8

11.     Sample Analysis

       11.1   Sample  Preparation

             11.1.1   The  samples  are returned to the laboratory in
                     50 ml  screw-capped glass vials.  To recover the
                     DNPH derivatives the following procedure is em-
                     ployed.
             11.1.2   The vials are shaken in a horizontal position on
                     a reciprocating shaker for 10 minutes.  The vials
                     are then removed from the shaker and the isooctane
                     layer  is removed and placed in a second clean 50 ml
                     screw-capped glass vial  using a disposable pipette.
             11.1.3   The remaining aqueous layer is extracted with 10 ml
                     of 70/30 (V/V) hexane/methylene chloride in the
                     same manner as described in 11.1.2.   The organic
                     layer is removed and combined with  the isooctane
                     extract.
             11.1.4   The combined organic extracts  are  then concentrated
                     to dryness  at 40°C  under a  steam of  pure nitrogen.
                     When  the sample  just reaches  dryness the vial  is
                     removed from the nitrogen  stream and a measured
                     volume  (2-5 ml)  of methanol is added to  the vial.
                     The vial  is tightly capped and stored refrigerated
                     until analysis.

      11.2   HPLC Analysis

            11.2.1    The instrument is assembled and calibrated as described
                     in Section 12.   Prior to each analysis the detector
                     baseline  is checked to ensure stable operation.
            11.2.2    A 5-25  ML aliquot of the sample, dissolved in
                     methanol.is drawn into a clean HPLC injection syringe.
                     The sample injection loop is loaded and an injection
                     is made.  The data system, if available, is activated
                     simultaneously with the injection and the point of
                     injection is marked on the stripchart recorder.

-------
                             T05-9

            11.2.3   After approximately one minute, the injection valve
                     is returned to "load" position and the syringe and
                     valve are flushed with methanol in preparation for
                     the next sample analysis.
            11.2.4   After elution of the last component of interest the
                     acquisition is terminated and the component concen-
                     trations are calculated as described in Section 13.
            11.2.5   After a stable baseline is achieved the system can
                     be used for further  sample analyses as described above.
            11.2.6   If the concentration of a component exceeds the linear
                     range of the instrument the  sample should  be diluted
                     with methanol, or  a  smaller  volume can be  injected
                     onto the HPLC.

12.     HPLC Assembly and Calibration

       12.1  The HPLC system  is  assembled  as shown in  Figure 3.   The
             typical chromatographic  performance  and operating  para-
             meters  are shown  in Figure  4.
       12.2  Mobile  phase  is  prepared  by mixing 800 mL of  methanol  and
             200 mL  of reagent water.   This  mixture is filtered through
             a 0.22  vm polyester membrane filter in an all  glass and
             teflon  suction  filtration apparatus.   The filtered mobile
             phase  is degassed by purging with helium  gas  for  10-15
             minutes (* 100 mL/minute) or by heating to ^60°C  for  5-10
             minutes in an Erlenmeyer flask covered with a watch glass.  A
             constant back pressure restrictor (* 50 psi)  or short length
             (6-12  inches) of 0.01 inch I.D. teflon tubing should be
             placed after the detector to further eliminate mobile phase
             outgassing.
       12.3  The mobile phase is placed in  the HPLC solvent reservoir and
             the pump  flow is set at  1 mL/minute  and allowed to  pump
             for 20-30 minutes  prior  to the first analysis.  The detector
             is switched on at  least  30 minutes prior  to the first
             analysis  and the detector  output  is  displayed on  a  stripchart
             recorder  or similar output device at a sensitivity of  .008

-------
                         T05-10

       absorbance units full scale (AUFS).   Once a stable baseline
       is achieved the system is ready for  calibration.
 12.4  Calibration standards are prepared in methanol  from the
       solid DNPH derivatives.   Individual  stock solutions of
       *• 100 mg/L are prepared  by dissolving 10  mg of  the solid
       derivative in  100 mL  of  methanol.  These  individual  solutions
       are used  to prepare calibration standards  containing all of
       the derivatives of interest at  concentrations of 0.1 -  10 mg/L
       which spans the concentration of interest  for most ambient
       air work.
 12.5   All  calibration runs  are  performed as described for sample
       analyses  in Section 11.   Before  initial use  the operator
       should  inject  a series of calibration standards (at least
       three levels)  spanning the  concentration range of  interest.
       Using the  UV detector, a linear  response range of approximately
       0.1  to  10  mg/L  should be  achieved, for * 10 VL injection
       volumes.   Linear response  is indicated where a correlation
       coefficient of  a least 0.999 for a linear least squares
       fit  of  the  data  (concentration versus area response) is
       obtained.
12.6  Once  linear response has  been documented an intermediate
      concentration standard near the  anticipated levels  for  each
      component, but at least 10 times the  detection limit, should
      be chosen  for daily calibration.  The response for  the  various
      DNPH components should be within 10%  day to day.   If greater
      variability is  observed more frequent calibration may be
      required to ensure that valid results are  obtained.
12.7  The response for each  component  in  the daily calibration
      standard is used to calculate a  response factor  according
      to the following equation:

                        Cc X VI
                RFc = 	£	1	
                          Rc

-------
                             T05-11
            where
                      RF  = response factor for the component of
                            interest in nanograms injected/response
                            unit  (usually area counts).
                      C   = concentration of component in the daily
                            calibration standard  (mg/L).
                      V   = volume  of  calibration standard injected  (uL)
                      R   = response for component  of  interest  in
                            calibration standard  (area counts).
13.     Calculations
       13.1   The volume of air sampled is often reported uncorrected for
             atmospheric conditions (i.e. under ambient conditions).
             However, the value can be adjusted to standard conditions
             (25°C and 760 mm pressure) using the following equation:

                                          P.       298
                                  Vsx  Vm x -2-  x	
                                         760    273 + T.
             where
                       Vs = total sample volume at 25°C and 760 mm Hg
                            pressure (liters).
                       Vm = total sample volume under ambient conditions
                            (liters).  Calculated in 10.9 or from dry gas
                            meter reading.
                       PA * ambient pressure  (nmHg).
                       T/\ = ambient temperature (°C).

        13.2   The  concentration  of each aldehyde (as  the  DNPH derivative  is
              calculated  for each sample  using the following equation:

-------
                        T05-12
                   Wd = RFc X Rd X ~
                                   VI
       where
                Wrf   =  total  quantity  of  derivative  in  the  sample
                RFc  =  response  factor calculated in  12.7
                Rd   =  response  for component in sample extract
                      (area counts or other response units).
                VE   =  final volume of sample extract (mL).
                Vj   =  volume of extract injected onto the HPLC
                      system (yL).
 13.3  The concentration of aldehyde in the original  sample  is
      calculated from the following equation:
                          W.          MW.
                 C  =	  X  -A-  X  1000
                       Hn(°r Vs )     MWd
      where

               CA = concentration of aldehyde in  the original
                    sample (ng/L).
               1|n  or Vs   are  as specified in Section 13.1.
               MWA and MWd are the  molecular  weights (g/mole) of
               the aldehyde and its  corresponding  DNPH  derivative,
               respectively.
13.4  The aldehyde concentrations  can  be  converted to ppbv  using
      the following equation:
                                       24.4
                  C.(ppbv) = C.(ng/L)  X 	
                                       MWA

      where

               CA(ng/L)  is calculated using Vs.

-------
                                T05-13

14.    Performance Criteria and  Quality  Assurance

       This section summarizes the quality assurance (QA)  measures  and
       provides guidance concerning performance criteria which  should
       be achieved within each laboratory.

       14.1  Standard Operating Procedures (SOPs).

             14.1.1   Each user should generate SOPs describing the
                      following activities as accomplished in their
                      laboratory:  1) assembly, calibration and operation
                      of the  sampling system, 2)  preparation, purification,
                      storage and handling of  DNPH  reagent and samples, 3)
                      assembly, calibration  and operation of the HPLC
                      system, and 4)  all  aspects  of data  recording and
                      processing.
              14.1.2   SOPs should provide specific  stepwise  instructions
                       and should  be readily  available to, and  understood
                       by, the laboratory personnel  conducting  the  work.


         14.2   HPLC System Performance

               14.2.1    The general appearance of  the  HPLC chromatograph
                        should be  similar  to  that  shown  in Figure 4.
               14.2.2    The HPLC system  efficiency and peak asymmetry
                        factor should  be determined  in the following manner.
                        A solution of  the  formaldehyde DNPH derivative cor-
                        responding to  at least  20  times  the detection
                        limit should be  injected with the  recorder  chart
                        sensitivity and  speed set  to yield a  peak
                        approximately 75% of  full  scale and  1  cm wide  at
                        half height.   The peak asymmetry factor is  determined
                        as shown in Figure 5, and  should be between
                        0.8 and 1.8.

-------
                         T05-14
       14.2.3   HPLC system efficiency is  calculated  according  to
                the following equation:
               where
                    N = column efficiency, theoretical plates
                    tr= retention time of components (seconds)
                    V/i/2 = width of component peak at half height
                        (seconds)
               A column efficiency of >5,000 should be obtained.
      14.2.4   Precision of response for replicate HPLC injections
               should be ± 10% or less, day to day, for calibration
               standards.   Precision of retention times should be
               ± 2%, on a  given day.


14.3  Process Blanks

      14.3.1    Prior to  use  a  10  mL  aliquot of each batch of  DNPH
               reagent  should  be  analyzed  as  described  in Section
               11.   In  general,formaldehyde levels  equivalent  to
               >5 ng/L  in a  60 liter sample should  be achieved
               and other aldehyde  levels should be  <1 ng/L.
      14.3.2    At least  one  field  blank should  be shipped and
               analyzed  with each  group of samples.  The field
               blank is  treated identically to  the  samples except
               that  no air is  drawn  through the reagent.  The
               same  performance criteria described  in 14.3.1
               should be met for process blanks.

-------
                         T05-15
14.4  Method Precision and Accuracy

      14.4.1   Analysis of replicate samples indicates a pre-
               cision of + 15-20% relative standard deviation
               can be readily achieved.  Each laboratory should
               collect parallel samples periodically (at least one
               for each batch of samples) to document their
               precision  in conducting the method.
       14.4.2   Precision  for replicate HPLC injections  should
               be i  10%  or better,  day to day, for calibration    ,
               standards.
       14.4.3  Method accuracy is  difficult to assess  because  of
                the  difficulty  in  generating accurate  gaseous
                standards.  Literature results  indicate (1-3)
                recoveries of 75% or greater are  achieved for a
                broad range of aldehydes.  Each laboratory should
                periodically collect field samples wherein the
                impinger solution is spiked with a known quantity
                of the compound of  interest, prepared as a dilute
                methanol  solution.  Formaldehyde cannot be spiked
                in this manner  and  therefore a solution of the DNPH
                derivative should  be  used for spiking  purposes.
        14.4.4   Before initial use of the method each laboratory
                 should generate triplicate spiked samples at  a minimum
                 of  three  concentration  levels,  bracketing the
                 range of  interest  for each compound.   Triplicate
                 nonspiked samples  must  also be  processed.   Recover-
                 ies of  >70 ±  20%.and blank  levels of  <5  ng/L  for
                 formaldehyde  and  1 ng/L for the other compounds
                  (assuming a 60 liter air sample)  should be  achieved.

-------
                                T05-16


                              References

      /iiHoh^   •  '*u  1-  K;'  and Atkinson»  R-«  "Measurements of

      A's^c^laJer^-SO1^^!^^1"'  "^ Al>  Po11' <""•

 (2)   Grosjean,  D.  and  Fung  K.,  "Collection  Efficiencies of Cartridges
      and  Micro-Impingers  for  Sampling of Aldehydes in Air as 2,J- §
      Dinitrophenylhydrazones",  Anal. Chem.  54,  1221-1224, 1982

 (3)   ?mM«naVD'''  "Formalde!!yde  and Other  Carbonyls in Los Angeles
      Ambient Air",  Environ. Sci.  Techno!. ]6, 254-262, 1982.

      IJ?lc,!eR'*M;t '!'Te^hn1cal  Assistance Document for Sampling and
       S  Envi         Organic  Compounds in Ambient Air",  EPA-600/4-83-027
 (5)  Annual Book of ASTM Standards, Part 11.03, "Atmospheric Analysis"

              SCle0r ^^ ^ »™«' ^           "^ '
     Snirp' °r Au' H°Jdr?n' M"  W" Lyon' T'  F"  Rl'99in.  R-  M. .  and
     Spicer, C  W .,  Turbine Engine Exhaust  Hydrocarbon  Analysis-Interim
     Report on Task 1  and 2", Report on Contract No.  F-08635-82-C-OT3"
     ^983      En9ineering and  Services Center,  Tyndall  AFB,  Florida,  '


(7)  Shiner, R   Fuson,  R   and Curtin, D. ,  "The Systematic  Identification
                          ' John Wile^ and Sons, Inc., 5th ed. , New
(8)   "Method  6  Determination of  S02  Emissions from Stationary Sources",
      Federal Register,  Vol. 42., No.  160, August 1977.

-------
                                  T05-17
  TABLE .1.  ALDEHYDES AND KETCHES FOR WHICH THE METHOD HAS BEEN EVALUATED
                                  Mnlecular Weight
                                  ^™^~   « _ _
                                                                 Typical
                                                                Relative
                                                                Retention
      Compound
Formaldehyde
Acetaldehyde
Acrolein
Propanal
Acetone
Crotonaldehyde
 Isobutyraldehyde
 Methyl  Ethyl  Ketone
 Benzaldehyde
 Pentanal
 o-Tolualdehyde
 m-Tolualdehyde
 p-Tolualdehyde
 Hexanal
Derivative
210
224
236
238
238
250
252
252
286
266
300
300
300
280
Compound.
30
44
56
58
58
70
72
72
106
86
120
120
120
100
1.0
1.3
1.6
1.7
l.g(b)
2.3
2.4
2.8
 3.2
 3.7
 4.8
 5.1
 5.3
 5.7
  (b)   Acetone background  levels in  the reagent prevent its  determination
       in most cases.

-------
                                                                           Silica Gel
                             Rotometer
              Dry

              Test
Vent
                                                             Pump
                                           Valve
                                                                                                              Sample Impinger	

                                                                                                              (DNPH Reagent)    /
                                                                                                                              Inlet
O
en
 i


00
                                                  FIGURE 1.  TYPICAL SAMPLING SYSTEM

-------
                                        T05-19
                                SAMPLING DATA SHEET
                            (One Sarole Per Data Sheet)
PROJECT:.

SITE:
                                               DATE(S)  SAMPLED:.
LOCATION:
TIME PERIOD SAMPLED:.

OPERATOR:	
INSTRUMENT MODEL NO:.

PUMP SERIAL NO:	

SAMPLING DATA
                                               CALIBRATED BY:
                        Sample Number:.

                 Start Time:  	
 Stop Time:
Time
1
2
3.
4
N. 	
Dry Gas
Meter
Reading





Rotameter
Reading





Flow
Rate,*Q
ml/Min





Ambient
Temperature
°C





Barometric
Pressure,
mmHg





Relative
Humidity, %





Comments





    Total Volume Data**
            Vm =  (Final  -  Initial)  Dry Gas Meter Reading, or

                  Ql  + Q?  + Q3---QN         1	
               =  _'	R	 x 1000 x (Sampling Time in Minutes)
                                  Liters

                                  Liters
      * Flowrate from rotameter or soap  bubble  calibrator
        (specify which).
     ** Use data from dry gas meter if available.
                       FIGURE 2.  EXAMPLE SAMPLING DATA SHEET

-------
                       INJECTION
                         VALVE
                                       COLUMN
 MOBILE
 PHASE
RESERVOIR
1 VARIABLE
WAVELENGTH
UV
DETECTOR


• •
DATA
SYSTEM

                                                                                        o
                                                                                        en
                                                                                        ro
                                                                                        o
STRIPCHART
 RECORDER
                          FIGURE 3. TYPICAL HPLC SYSTEM

-------
                                                                                       o
                                                                                       en
                                                                                       i
                                                                                       ro
2 0
40
60
                   FIGURE 4.  TYPICAL HPLC CHROMATOGRAM

                               Column  -  Zorbax  ODS,  250  x  4.6 mm

                               Mobile  Phase  - 80/20  Methanol/^O

                               Flow Rate -  1 ml/Minutc

                               Detector  - UV at 370  nm

-------
               T05-22
         Asymmttry Factor » ?£.
                          AB
Example Calculation:

    Paak Height - OE - 100 mm
    10% Peak Height - 80 - 10 mm
    Paak Width at 10% Paak Height » AC - 23 mm
         AB- 11 mm
         BC *12mm

    Tharafora:  Aiymmatry Factor - ~ » 1.1
FIGURE 8. PEAK ASYMMETRY CALCULATION

-------
APPENDIX A— EPA METHOD 608
                               Environmental Monitoring and

   Research and Development
   Test Method
   Organochlorine  Pesticides
   and  PCBs  —  Method  608
   1.   Scope and Application

   1.1  This method covers the
   determination of certain organochlorine
   pesticides and PCBs. The following
   parameters can be determined by this
   method:
Parameter
Aldrin
a-BHC
0-BHC
d-BHC
y-BHC
Chlordane
4, 4 '-ODD
4,4 '-DDE
4,4 '-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCS- 12 54
PCB-1260
STORET No.
39330
39337
39338
34259
39340
39350
39310
39320
39300
39380
34361
34356
34351
39390
34366
39410
39420
39400
34671
39488
39492
39496
39500
39504
39508
CAS No.
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
959-98-8
33212-65-9"
1031-07-8
72-20-8
7421-93-4
76-44-8
1024-57-3
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
1 2  This is a gas chromatographic
(GO method applicable to the determi-
nation of the compounds listed above
in municipal and industrial discharges
M provided under 40 CFR 1 36. 1 .
When this method is used to analyze
unfamiliar samples for any or all of the
compounds above, compound idenf.fi-
cations should be supported by at least
                                one additional qualitative technique.
                                This method describes analytical
                                conditions for a second gas
                                chromatographic column that can be
                                used to confirm measurements made
                                with the primary column. Method 625
                                provides gas ch~™tc^rapWrnass
                                spectrometer (GC/MS) condjt.ons
                                appropriate for the qualitative and
    608-1
                            1982

-------
   quantitative confirmation of results for
   all of the parameters listed above,
   using the extract produced by this
   method.

   1.3  The method detection limit (MDL,
   defined in Section 14.1)<1> for each
   parameter is listed in Table 1. The MDL
   for a specific wastewater may differ
   from those listed, depending upon the
   nature of interferences in the sample
   matrix.

   1.4  The sample extraction and
  concentration steps in this method are
  essentially the same as in methods
  606, 609, 611  and 612. Thus, a
  single sample may be extracted to
  measure the parameters included in  the
  scope of each of these methods. When
  cleanup is required, the concentration
  levels must be high enough to permit
  selection of aliquots as necessary to
 .apply appropriate cleanup procedures.
  The analyst is allowed the latitude to
  select gas chromatographic conditions
  appropriate for the simultaneous
  measurement of combinations of these
  parameters.

  1.5   Any modification of this method,
  beyond those expressly permitted,
  shall be considered as major
 modifications subject to application
 and approval of alternate test
 procedures under 40 CFR 1 36 4 and
  136.5.

  1.6   This method is restricted to use
 by or under the supervision of analysts
 experienced in the use of gas chroma-
 tography and in the interpretation of
 gas chromatograms. Each analyst must
 demonstrate the  ability to generate
 acceptable results with this method
 using the procedure described in
 Section 8.2.


 2.  Summary of Method

 2.1  A measured volume of sample,
 approximately one-liter, is solvent
 extracted with methylene chloride
 using a separatory funnel. The
 methylene chloride extract is dried and
 exchanged to hexane, during
 concentration to a final volume of 10
 ml or less. Gas chromatographic
 conditions are described which permit
 the separation and measurement of the
 parameters in the  extract by electron
capture GCI2>.

 2.2  The method provides a Florisil
 column procedure and elemental sulfur
 removal procedure to aid in the
elimination of interferences that may
be encountered.
   3.  Interferences
   3.1   Method interferences may be
   caused by contaminants in solvents,
   reagents, glassware, and other sample
   processing hardware that lead to
   discrete artifacts and/or elevated
   baselines in gas chromatograms. All of
   these materials must be routinely
   demonstrated to be free from inter-
   ferences  under the conditions of the
   analysis by running laboratory reagent
   blanks as described  in Section 8.5.

  3.1.1  Glassware must be scrupulously
  cleanedi3i. Clean all glassware as soon
  as possible  after use by rinsing with the
  last solvent used in it. This should be
  followed  by detergent washing with
  hot water, and rinses with tap water
  and distilled water. It should then be
  drained dry and heated in a muffle
  furnace at 400 °C for 1 5 to 30
  minutes. Some thermally stable
  materials, such as PCBs, may not be
  eliminated by this treatment. Solvent
  rinses with acetone and pesticide
  quality hexane may be substituted for
  the muffle furnace heating. Thorough
  rinsing with such solvents usually
  elmmates PCB interference. Volumetric
  ware should not be heated in a muffle
  furnace. After drying and cooling,
  glassware should be sealed and stored
  in a clean  environment to prevent any
  accumulation of dust or other
  contaminants. Store inverted or capped
  with aluminum foil.

 3.1.2   The use of high purity reagents
 and solvents helps to minimize
 interference problems. Purification of
 solvents by distillation in all-glass
 systems may be required.
 3,2  Interferences by phthalate esters
 can pose a major problem in pesticide
 analysis when using the elution capture
 detector. These compounds generally
 appear in the chromatogram as large
 eluting peaks, especially in the 1 5 and
 50% fractions from Florisil. Common
 flexible plastics contain varying
 amounts of phthalates. These phtha-
 lates are easily extracted or leached
 from such materials during laboratory
 operations. Cross contamination of
 clean glassware routinely occurs when
 plastics are handled during extraction
 steps, especially when solvent wetted
 surfaces are handled. Interferences
 from phthalates can best be minimized
 by avoiding the use of plastics in the
 laboratory.  Exhaustive cleanup of
 reagents and glassware may be
 required to  eliminate background
 phthalate contamination!4.5i. Tne
 interferences from phthalate esters can
be avoided  by using a microcoulometric
or electrolytic conductivity detector.
   3.3  Matrix interferences may be
   caused by contaminants that are
   coextracted from the sample. The
   extent of matrix interferences will vary
   considerably from source to source,
   depending upon the nature and
   diversity of the industrial complex or
   municipality being sampled. The
   cleanup procedures in Section 1 1 can
   be used to overcome many of these
   interferences, but unique samples may
   require additional cleanup approaches
  to achieve the MDL listed in Table 1.

  4.   Safety

  4.1   The toxicity or carcinogenicity of
  each reagent used in this method  has
  not  been precisely defined; however,
  each chemical compound should be
  treated as a potential health hazard.
  From this viewpoint, exposure to these
  chemicals must be reduced to the
  lowest possible level by  whatever
  means available. The laboratory is
  responsible for  maintaining a current
  awareness file of OSHA  regulations
  regarding the safe handling of the
  chemicals specified  in this method. A
  reference file of material data handling
  sheets should also be made available to
  all personnel involved in the chemical
  analysis. Additional  references to
  laboratory safety are available and
  have been identified'6-8) for tne
  information of the analyst.

 4.2  The following  parameters
 covered by this  method have been
 tentatively classified as known or
 suspected, human or mammalian
 carcinogens: 4,4'-DDT,4,4'-ODD,  the
 BHCs, and the PCBs. Primary
 standards of these toxic compounds
 should be prepared in a hood.

 5.   Apparatus and Materials

 5.1   Sampling equipment, for discrete
 or composite sampling.

 5.7.7  Grab sample  bottle —Amber
 glass, one-liter or one-quart volume,
 fitted with screw caps lined with
 Teflon. Foil may  be substituted for
 Teflon if the sample is not corrosive. If
 amber bottles are not available, protect
 samples from light. The container must
 be washed, rinsed with acetone or
 methylene chloride, and dried before
 use to minimize contamination.

 5.1.2 Automatic sampler (optional)-
 Must  incorporate glass sample
 containers for the collection of a mini-
 mum  of 250 mL. Sample containers
 must  be kept refrigerated at 4 °C and
protected from light during compositing.
If the  sampler uses a peristaltic pump,
a minimum length of compressible
                                      608-2
                                                                 July 1982

-------
silicone rubber tubing may be used.
Before use, however, the compressible
tubing should be thoroughly rinsed
with methanol, followed by repeated
rinsings with distilled water to minimize
the potential for contamination of the
sample. An integrating flow meter is
required to collect flow proportional
composites.
5.2  Glassware (All specifications are
suggested. Catalog numbers are
included for illustration only).

5.2.1  Separatory funnel-2000-mL,
with Teflon stopcock.

5.2.2  Drying column-Chroma-
tographic column approximately 400
mm long  x 1 9 mm ID, with coarse frit.

5.2.3  Chromatographic column —
Pyrex, 400 mm long x 22 mm ID,
with coarse fritted plate and Teflon
stopcock (Kontes  K-42054 or
equivalent).
 5.2.4  Concentrator tube, Kuderna-
 Danish— 10-mL, graduated (Kontes K-
 570050-1 025 or equivalent). Calibra-
 tion must be checked at the volumes
 employed in  the test. Ground glass
 stopper is used to prevent evaporation
 of extracts.
 5.2.5 Evaporative flask, Kuderna-
 Danish-500-mL (Kontes K-570001-
 0500 or equivalent). Attach to
 concentrator tube with springs.

 5.2.6  Snyder column, Kuderna-
 Danish-three-ball macro (Kontes
 K-503000-01 21 or equivalent).

 5.2.7  Vials-Amber glass, 10-to
  1 5-mL capacity, with Teflon-lined
 screw cap.
 5.3  Boiling chips-approximately
  10/40 mesh. Heat to 400 °C for 30
 minutes or Soxhlet extract with
 methylene chloride.
  5.4  Water bath —Heated, with
  concentric ring cover, capable of
 temperature control ( ± 2 °C). The bath
  should be used in a hood.

 5.5  Balance —Analytical, capable of
 accurately weighing 0.0001 g.

  5.6  Gas chromatograph —An
  analytical system complete with gas
  chromatograph suitable for on-column
  injection and all required accessories
  including syringes, analytical columns,
  gases, detector, and strip-chart
  recorder. A data system is
  recommended for measuring peak
  areas.
   5.6.7   Column 1-1.8 m long x 4
   mm ID glass, packed with 1.5%
SP-2250/1.95% SP-2401 on
Supelcoport (10011 20 mesh) or
equivalent. Column 1 was used to
develop the method  performance
statements in Section 14. Guidelines
for the use of alternate column
packings are provided in Section 12.1.

5.6.2   Column 2-1.8 m long x 4
mm ID glass, packed with 3% OV-1 on
Supelcoport (10011  20 mesh) or
equivalent:
5.6.3   Detector-Electron capture.
This detector has proven effective in
the analysis of wastewaters for the
parameters listed in the scope, and
was used to develop the method
performance statements in Section 14.
Guidelines for the use of alternate
detectors are provided in Section 12.1.

6.  Reagents
6.1   Reagent water-Reagent water is
defined as a water in which an inter-
ferent is not observed at1 the MDL of
each parameter of interest.

 6.2  Sodium hydroxide solution (10
 N)-(ACS). Dissolve 40g NaOH in
 reagent water and dilute to 1 00 ml.

 6.3  Sodium thiosulfate-(ACS).
 Granular.
 6.4  Sulfuric acid solution (1 + 1 )-
 (ACS). Slowly, add 50 ml H2S04 (sp.
 gr. 1.84) to 50  ml of reagent water.

 6.5  Acetone, hexane, isooctane
 (2,2,4-trimethylpentane), methylene
 chloride-Pesticide quality or
 equivalent.
 6.6   Ethyl ether- Pesticide quality or
 equivalent, redistilled in glass if
 necessary.
 6.6.7   Must be free of peroxides as
 indicated by EM Laboratories Quant
 test strips (Available from Scientific
 Products Co., Cat.  No. P1 1 26-8, and
 others suppliers.)
 6.6.2  Procedures recommended for
 removal of peroxides are provided with
 the test strips. After cleanup, 20  ml
 ethyl alcohol preservative must be
 added to each liter of ether.
 6.7  Sodium sulfate-(ACS) Granular,
 anhydrous. Purify by heating at 400 °C
 for 4 hours in a shallow tray.

  6.8  Florisil-PR grade (60/1 00
  mesh); purchase activated at 1 250 °F
  and store in dark in glass containers
  with glass stoppers or foil-lined screw
  caps.  Before use, activate each batch
  at least  16 hours at 1 30 °C in a foil
  covered glass container.

  6.9   Mercury —Triple distilled.
6.10  Copper powder-Activated.

6.11  Stock standard solutions (1.00
^ig/nD-Stock standard solutions can
be prepared from pure standard
materials or purchased as certified
solutions.
6.77.7   Prepare stock standard
solutions by accurately weighing about
0.01 00 grams of pure material.
Dissolve  the material in isooctane,
dilute to volume in a 10-mL volumetric
flask. Larger volumes can be  used at
the convenience of the analyst. If
compound purity is certified at 96% or
greater, the weight can be used
without correction to calculate the
concentration of the stock standard.
Commercially  prepared stock standards
can be used at any concentration if
they are  certified by the manufacturer
or by an  independent source,
 6.77.2  Transfer the stock  standard
 solutions into Teflon-sealed screw-cap
 bottles. Store at 4 °C and protect from
 light. Stock standard solutions should
 be checked frequently for signs of
 degradation or evaporation,  especially
 just prior to preparing calibration
 standards from them. Quality control
 check standards that can be used to
 determine the accuracy of calibration
 standards will be available from the
 U.S. Environmental Protection Agency,
 Environmental Monitoring and Support
 Laboratory, Cincinnati, Ohio 45268.

 6.77.3   Stock standard solutions
 must be replaced after six months, or
 sooner if comparison with check
 standards indicate  a problem.

 7.  Calibration

 7.1   Establish gas Chromatographic
 operating parameters which produce
 retention times equivalent to those
 indicated in Table 1. The gas
 Chromatographic system may be
 calibrated using the external standard
 technique (Section 7.2) or the internal
 standard technique (Section 7.3).

 7.2  External standard calibration
 procedure:
  7.2. 7  Prepare calibration  standards
 at a minimum of three concentration
  levels for each parameter of interest by
  adding  volumes of one or more stock
  standards to a volumetric flask and
  diluting to volume with isooctane. One
  of the external standards should be at a
  concentration near, but above, the
  MDL and the other concentrations
  should correspond to the expected
  range of concentrations found in real
  samples or should define the working
  range of the detector.
                                        608-3
                                                                    July 1982

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  7.2.2  Using injections of 2 to 5 ^L of
  each calibration standard, tabulate
  peak height or area responses against
  the mass injected. The results can be
  used to prepare a calibration curve for
  each compound. Alternatively, if the
  ratio of response to amount injected
  (calibration factor) is a constant over
  the working range «10% relative
  standard deviation, RSD), linearity
  through the origin can be assumed and
  the average ratio or calibration factor
  can be used in place of a calibration
  curve.

  7.2,3  The working calibration curve
  or calibration  factor must be verified on
  each working day by the measurement
  of one or more calibration standards. If
 the response for any parameter varies
 from the predicted response by more
 than ± 10%,  the test must be repeated
 using a fresh calibration standard.
 Alternatively,  a new calibration curve
 o.r calibration factor must be prepared
 for that compound.

 7.3  Internal  standard calibration
 procedure. To use this approach, the
 analyst must select one or more
 internal standards that are similar in
 analytical behavior to the compounds
 of interest. The analyst must further
 demonstrate that the measurement of
 the internal standard is not affected by
 method or  matrix interferences.
 Because of these limitations,  no
 internal standard can be suggested that
 is applicable to all samples.

 7.3. 1   Prepare calibration standards
 at a minimum  of three concentration
 levels for each parameter of interest by
 adding volumes of one or more stock
 standards to a volumetric flask.  To
 each calibration standard, add a known
 constant amount of one or more
 internal standards, and dilute to volume
 with isooctane. One of the standards
 should be at a  concentration near, but
 above, the  MDL and the other concen-
 trations should correspond to the
 expected range of concentrations
 found in real samples or should define
the working range of the detector.
7.3.2  Using injections of 2 to 5 pi of
each calibration standard, tabulate
peak height or area responses against
concentration for each compound and
internal standard, and calculate
response factors (RF) for each
compound using equation 1 .

     Eq.  1.  RF = (ASC1S)/!A,SCS)
where:
  As  =  Response for the parameter to
        be measured.
  AI8  =  Response for the internal
        standard.
    Cls = Concentration of the internal
          standard, (^g/L).
    Cs = Concentration of the param-
          eter to be measured, (jig/L).

    If the RF value over the  working
  range is a constant «1 0% RSD), the
  RF can be assumed to be invariant and
  the average RF can be used for
  calculations. Alternatively, the results
  can be used to plot a calibration curve
  of response ratios, AS/AIS, vs. RF.

  7.3.3   The working  calibration curve
  or RF must be verified on each working
  day by the measurement of one or
  more calibration standards. If the
  response for any parameter varies from
  the predicted response by  more than
  ± 1 0%, the test must be repeated
  using a fresh calibration standard.
  Alternatively, a new calibration curve
  must be prepared for  that compound.

  7.4 The cleanup procedure in Section
  11  utilizes Florisil chromatography.
  Florisil from different  batches or
  sources may vary in absorptive
 capacity. To standardize the amount of
 Florisil which is used, the use of lauric
 acid valued is suggested.  The refer-
 enced procedure determines the
 adsorption from hexane solution of
 lauric acid (mg) per gram Florisil. The
 amount of Florisil to be used for each
 column is calculated by dividing this
 factor into 1 10 and multiplying by 20
 g.

 7.5  Before using any cleanup
 procedure, the analyst must process a
 series of calibration standards through
 the procedure to validate elution
 patterns and the absence of interfer-
 ences from the reagents.

 8.   Quality Control

 8.1   Each laboratory that uses this
 method is required to operate a formal
 quality control program. The minimum
 requirements of this program consist of
 an initial demonstration of laboratory
 capability and the analysis of spiked
 samples as a continuing check on
 performance. The laboratory is required
 to maintain performance records to
 define the quality of data that is
 generated. Ongoing  performance
 checks must be compared with
 established performance criteria to
 determine if the results of analyses are
 within accuracy and precision limits
 expected of the method.

S. 1.1  Before performing any analyses,
the analyst must demonstrate the
ability to generate acceptable accuracy
and precision with this method. This
ability is established as described in
Section 8.2.
  8.1.2  In recognition of the rapid
  advances that are occurring in chroma-
  tography, the analyst is permitted
  certain options to improve the separa-
  tions or lower the cost of measurements.
  Each time such modifications are made
  to the  method,  the analyst is required
  to repeat the procedure in Section 8.2.

  8.1.3  The laboratory must spike and
  analyze a minimum of 1 0% of all
  samples to monitor continuing labora-
  tory performance. This procedure is
  described in Section 8.4.

  8.2  To establish the ability to
  generate acceptable accuracy and pre-
  cision, the analyst must perform the
  following operations.

  8.2.1  Select a representative spike
  concentration for each compound to be
 measured. Using stock standards,
  prepare a quality control check sample
 concentrate in acetone 1 000 times
 more concentrated than the selected
 concentrations. Quality control check
 sample concentrates, appropriate for
 use with this method, will be available
 from the U.S. Environmental Protection
 Agency, Environmental Monitoring and
 Support Laboratory, Cincinnati, Ohio
 45268.
 8.2.2  Using a  pipet, add 1.00 ml of
 the check sample concentrate to each
 of a minimum of four  1000-mL aliquots
 of reagent water. A representative
 wastewater may be used in place of
 the reagent water, but one or more
 additional aliquots must be analyzed to
 determine background levels, and the
 spike level must exceed twice the
 background level for the test to be
 valid. Analyze the aliquots according to
 the method  beginning in Section 10.

 8.2.3  Calculate the average percent
 recovery, (R), and the standard devia-
 tion of the percent recovery (s), for the
 results. Wastewater background cor-
 rections must be made before R and s
 calculations are performed.

 8.2.4  Using Table 2, note the
 average recovery (X) and standard
 deviation (p) expected for each method
 parameter, Compare these to the cal-
 culated  values for R and s. If s > 2p or
 |X-R > 2p, review potential problem
 areas and repeat the test.

 8.2.S  The  U.S. Environmental Pro-
 tection Agency plans to establish
 performance criteria for R and s based
 upon the results  of interlaboratory
testing.  When they become available,
these criteria must be met before any
samples may be analyzed.

8.3   The analyst must calculate
method  performance criteria and define
                                      6Q8-4
                                                                  July 1982

-------
the performance of the laboratory for
each spike concentration and
parameter being measured.

8.3.1  Calculate upper and lower
control limits for method performance:

  Upper Control Limit (UCL)  = R + 3s
  Lower Control Limit (LCD  = R - 3s

where R and s are calculated as in
Section 8.2.3. The UCL and LCL can
be used to construct control charts'101
that are useful in observing  trends in
performance. The control limits above
be replaced by method performance
criteria as they become available from
the U.S. Environmental Protection
Agency.
8.3.2  The laboratory must develop
 and maintain separate accuracy
 statements of laboratory performance
 for wastewater samples. An accuracy
 statement for the method is defined as
 R ± s. The accuracy statement should
 be developed by the analysis of four
 aliquots of wastewater as described in
 Section  8.2.2, followed by the calcula-
 tion of R and s. Alternately, the analyst
 may use four wastewater data points
 gathered through the requirement for
 continuing quality control in Section
 8.4. The accuracy statements should
 be updated regularly! 10>.

  8.4.  The laboratory is required to
  collect a portion of their samples in
  duplicate to monitor spike  recoveries.
  The frequency of spiked sample analysis
  must be at least 10% of all samples or
  one sample per month, whichever is
  greater. One aliquot of the sample must
  be spiked and analyzed as described in
  Section 8.2. If the recovery for a
  particular parameter does  not fall
  within the control limits for method
  performance, the results reported for
  that parameter in all samples  processed
  as part of the same set must be quali-
  fied as described in Section 1 3.5. The
  laboratory should monitor the frequency
  of data so qualified to ensure that it
  remains at or below 5%.

  8.5  Before processing any samples,
  the analyst should demonstrate through
  the analysis of a one-liter aliquot of
  reagent water,^that all glassware and
  reagent interferences are under control.
  Each time a set of samples is extracted
  or there is a  change in reagents, a
  laboratory reagent blank should be
  processed as a safeguard  against
  laboratory contamination.

   8.6  It is recommended that the
   laboratory adopt additional quality
   assurance practices for use with this
   method. The specific practices that are
   most productive depend upon the
needs of the laboratory and the nature
of the samples. Field duplicates may be
analyzed to monitor the precision of
the sampling technique. When doubt
exists over the identification of a peak
on the chromatogram, confirmatory
techniques such as gas chromatography
with a dissimilar column, specific
element detector, or mass spectrometer
must be used. Whenever possible, the
laboratory should perform analysis of
standard reference materials and parti-
cipate in relevant performance
evaluation studies.

9.  Sample Collection,
Preservation, and Handling
9.1   Grab samples must be collected
in glass containers. Conventional
sampling practices!1 n should  be
followed, except that the bottle must
not be prewashed  with sample before
collection. Composite samples should
be collected in refrigerated glass
containers in accordance with the
requirements of the program. Automatic
sampling  equipment  must be as free as
 possible of Tygon  tubing and other
 potential  sources of contamination.

 9.2  The samples must be iced or
 refrigerated at 4 °C from the time of
 collection until extraction. If the
 samples will not be extracted within
 72 hours of collection, the sample
 should be adjusted to a pH range of
 5.0 to 9.0 with sodium hydroxide or
 sulfuric acid. Record the volume of acid
 or base used. If aldrin is to be
 determined, add sodium thiosulfate
 when residual chlorine is present. U.S.
 Environmental Protection Agency
 methods 330.4 and 330.5 may be
  used to measure chlorine residual'12|.
  Field test kits are  available for this
  purpose.
  9.3  All samples must be extracted
  within 7 days and completely analyzed
  within 40 days of extraction^'.

  10.   Sample Extraction

  10.1  Mark the water meniscus on the
  side of the sample bottle for later deter-
  mination of sample volume. Pour the
  entire sample into a two-liter separatory
  funnel.
  10.2  Add 60 mL methylene chloride
  to the sample bottle, seal, and shake
  30 seconds to rinse the inner surface.
  Transfer the solvent to the separatory
  funnel and extract the sample by
  shaking the funnel for two minutes
  with periodic venting to release excess
  pressure. Allow the organic  layer to
  separate from the water phase for a
  minimum of TO minutes. If the emulsion
  interface between layers is more than
one-third the volume of the solvent
layer, the analyst must employ me-
chanical techniques to complete the
phase separation. The optimum tech-
nique depends upon the sample, but
may include stirring, filtration of the
emulsion through glass wool, centrifu-
gation, or other physical methods.
Collect the methylene chioride extract
in a 250-ml. Erlenmeyer flask.

10.3  Add a second 60-mL volume of
methylene  chloride to the sample bottle
and repeat the extraction procedure a
second time, combining the extracts in
the Erlenmeyer flask. Perform a third
extraction  in the same manner.

 10.4  Assemble a Kuderna-Danish
 (K-D) concentrator by attaching a,
 10-mL concentrator tube to a 500-rnL
 evaporative flask. Other concentration
 devices or techniques may be used in
 place of the Kuderna Danish if the
 requirements of Section 8.2 are met.

 10.5  Pour the combined extract
 through a drying column containing
 about 10 cm of anhydrous sodium
 sulfate, and collect the extract in the
 K-D concentrator.  Rinse the Erlenmeyer
 flask and column with 20 to 30 ml of
 methylene chloride to complete the
 quantitative transfer.
 10.6   Add one or two clean boiling
 chips to the evaporative flask and
 attach a three-ball Snyder column.
 Prewet the Snyder column by adding
 about 1 ml. methylene chloride to the
 top. Place the K-D apparatus on a hot
  water bath (60 to 65 °C) so that the
  concentrator tube is partially immersed
  in the hot water and the entire lower
  rounded surface of the flask is bathed
  with hot vapor. Adjust the vertical
  position of the apparatus and the  water
  temperature as required to complete
  the concentration in 1 5 to 20 minutes.
  At the proper rate of distillation the
  balls of the column will actively chatter
  but the chambers will not flood with
  condensed solvent. When the apparent
  volume of liquid reaches 1 mL, remove
  the K-D apparatus and allow it to drain
  and cool for at least 1 0 minutes.
  10.7   Increase the temperature  of the
  hot water bath to about 80 °C.
  Momentarily remove the Snyder
  column, add 50 mL of hexane and a
  new  boiling chip and reattach the
  Snyder column. Prewet the column by
  adding about 1 mL of hexane to the
  top.  Concentrate the solvent extract as
  before. The elapsed time of concentra-
  tion should be 5 to 10 minutes. When
  the apparent volume of liquid reaches 1
  mL, remove the K-D apparatus and
  allow it to drain and cool at least 1 0
  minutes.
                                         608-5
                                                                    July 1982

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  10.8   Remove the Snyder column and
  rinse the flask and its lower joint into
  the concentrator tube with 1 to 2 ml
  of hexane, A 5-mL syringe is recom-
  mended for this operation. Stopper the
  concentrator tube and store
  refrigerated if further processing will
  not be performed immediately. If the
  extracts will be stored longer than two
  days, they should be transferred to
  Teflon-sealed screw-cap bottles. If the
  sample extract requires  no further
  cleanup, proceed with gas chromato-
  graphic analysis. If the sample requires
  cleanup proceed to Section 1 1.

  10.9  Determine the original sample
  volume by refilling the sample bottle to
  the mark and transferring the liquid to a
  1000-mL graduated cylinder. Record
  the sample volume to the nearest 5 ml.

  11.  Cleanup and Separation

  11.1  Cleanup procedures may  not be
 necessary for a relatively clean sample
 matrix. The cleanup procedures recom-
 mended in this method have been used
 for the analysis of various clean waters
 and industrial effluents. If particular
 circumstances demand the use of an
 alternative cleanup procedure, the
 analyst must determine the elution
 profile and demonstrate that the
 recovery of each compound of interest
 is no less than 85%. The Florisil
 column allows for a select fractionation
 of the compounds and will eliminate
 polar materials. Elemental sulfur
 interferes with the electron capture gas
 chromatography of certain pesticides,
 but can be removed by the techniques
 described below.

 11.2  Florisil column cleanup:

 11.2.1  Add a weight of Florisil
 (nominally 21 g) predetermined by cali-
 bration (Section 7.4 and 7.5), to  a
 chromatographic column. Settle the
 Florisil by tapping the column. Add
 sodium sulfate to the top  of the Florisil
 to form a layer 1 to 2 cm  deep. Add 60
 mL of hexane to wet and  rinse the
 sodium sulfate and Florisil. Just prior to
 exposure of the sodium sulfate to air,
 stop the elution of the hexane by
 closing the stopcock on the chroma-
 tography column. Discard the eluate.

 11.2.2  Adjust the sample extract
 volume to 10 mL with hexane and
 transfer it from the K-D concentrator
 tube to the Florisil column. Rinse the
 tube twice with 1 to 2 ml hexane,
 adding each rinse to the column.

 11.2.3  Place a 500-mL  K-D flask and
clean concentrator tube under the
chromatography column. Drain the
column into the flask until the sodium
  sulfate latyer is nearly exposed. Eiute
  the column with 200 ml of 6% ethyl
  ether in hexane (V/V) (Fraction 1) using
  a drip rate of about 5 mL/min. Remove
  the K-D flask and set aside for later
  concentration. Elute the column again,
  using 200 ml of  1 5% ethyl ether in
  hexane (V/VHFraction 2),  into a second
  K-D flask. Perform the third elution
  using 200 ml of 50% ethyl ether in
  hexane (V/VMFraction 3). The elution
  patterns for the pesticides an PCB's are
  shown in Table 2.

  /1.2.4  Concentrate the eluates by
  standard K-D techniques (Section
  10.6), substituting hexane for the
  glassware rinses and using the water
  bath at about 85 °C. Adjust final
  volume to 10 mL with hexane. Analyze
  by gas chromatography.

  11.3   Elemental sulfur will usually
  elute entirely in Fraction 1 of the Florisil
  column cleanup. To remove sulfur
  interference from this fraction or the
  original extract, pipet 1.00 mL of the
  concentrated extract into a clean con-
 centrator tube or Teflon-sealed vial.
 Add one to three drops of mercury and
 seald3i. Agitate the contents of the
 vial for 1 5 to 30 seconds. Prolonged
 shaking (two hours) may be required. If
 so, this may be accomplished with a
 reciprocal shaker. Alternatively,
 activated copper powder may be used
 for sulfur removal'!*). Analyze by gas
 chromatography.

 12.  Gas Chromatography

 12.1  Table 1 summarizes the
 recommended operating conditions for
 the gas chromatograph. This table
 includes retention times and MDL that
 were obtained under these conditions.
 Examples of the parameter separations
 achieved by column  1 are shown in
 Figures 1 to 10. Other packed
 columns, chromatographic conditions,
 or detectors may be used if the
 requirements of Section 8.2 are met.
 Capillary (open-tubular) columns may
 also be used if the relative standard
 deviations of responses for replicate
 injections are demonstrated to be less
 than 6% and the requirements of
 Section 8.2 are met.

 12.2  Calibrate the system daily as
 described in Section 7.

 12.3  If the internal standard
 approach is being used, the internal
 standard must be added to the sample
 extract and mixed thoroughly
 immediately, before injection into the
 instrument.

 12.4 Inject 2 to 5 j^L of the sample
extract using the solvent-flush
  technique'! 5). Smaller (1.0 ^iL) volumes
  can be injected if automatic devices are
  employed. Record the volume injected
  to the nearest 0.05 vL, the total
  extract volume, and the resulting peak
  size in area or peak height units.

  12.5  The width of the retention time
  window used to make identifications
  should be based upon measurements
  of actual retention time variations of
  standards over the course of a day.
  Three times the standard deviation of a
  retention time for a compound can be
  used to calculate a suggested window
  size; however, the experience of the
  analyst should weigh heavily in the
  interpretation of chromatograms.

  12.6  If the response for the peak
 exceeds the working range of the
 system, dilute the extract and
 reanalyze.

  12.7  If the measurement  of the peak
 response is prevented by the presence
 of interferences, further cleanup is
 required.

 13.  Calculations

 13.1  Determine the concentration of
 individual compounds in the sample.

 13.1.1  If the external standard
 calibration procedure is used, calculate
 the amount of material injected from
 the peak response using the calibration
 curve or calibration factor in Section
 7.2.2. The concentration in the sample
 can be calculated from equation 2:
Eq. 2. Concentration,
                            (A)(Vt)
                                 s
where:
  A =  Amount of material injected, in
        nanograms.
  V, =  Volume of extract injected
        (ML).
  V, =  Volume of total extract (^L).
  Vs =  Volume of water extracted
        (ml).

13. 1.2   If the internal standard cali-
bration procedure was used, calculate
the concentration in the sample using
the response factor (RF) determined in
Section  7.3.2 and equation 3.

Eq. 3

Concentration, Mg/L =
                         (At)(lt)
where:
  As  = Response for the parameter to
        be measured.
  Ajg  = Response for the internal
        standard.
  I,   = Amount of internal standard
        added to each extract (pg).
  V0  = Volume of water extracted, in
        liters.
                                      608-6
                                                                 July f982

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13.2  When it is apparent that two or
more PCB (Aroclor) mixtures are
present, the Webb and McCall
procedure1161 may be used to identify
and quantify the Aroclors.

13.3   For multicomponent mixtures
(chlordane, toxaphene and PCBs)
match retention times of peaks in the
standards with peaks in the sample.
Quantitate  every identifiable peak
unless interference with individual
peaks persist after cleanup. Add peak
height or peak area of each identified
peak  in the chromatogram. Calculate
as total response in the sample versus
total  response in the standard.

 13.4  Report results in micrograms
 per liter without correction for recovery
 data. When duplicate and spiked
 samples are analyzed, report all data
 obtained with the sample results.

 13.5  For samples processed as part
 of a set where the laboratory spiked
 sample recovery falls outside of the
 control limits in Section 8.3, data for
 the affected parameters must be
 labeled as  suspect.

 14.   Method Performance

 14.1  The method detection limit
 (MDU is defined as the minimum
 concentration of a substance that can
 be measured and reported with 99%
 confidence that the value is above
 zero!11. The MDL concentrations listed
 in Table 1  were obtained using reagent
 water<171.  Similar results were achieved
 using representative wastewaters.

  14.2  This method has been tested
 for linearity of spike recovery from
 reagent water and has been demon-
 strated to be applicable over the
 concentration range from 4 x MDL up
 to 1000  x MDL with the following
  exceptions: Chlordane recovery at 4  x
  MDL was low (60%); Toxaphene
  recovery was demonstrated linear over
  the range of 10 x MDL to 1000  x
  MDL<17>.

  14.3  In a single laboratory (South-
  west Research Institute),  using spiked
  wastewater samples, the average
  recoveries presented in Table 3 were
  obtained141. Each spiked sample was
  analyzed in triplicate on two separate
  days. The standard deviation of the
  percent recovery is also included in
  Table 3.

   14.4  The U.S. Environmental Protec-
  tion Agency is in the process of
   conducting an interlaboratory method
   study to  fully define the performance
   of this method.
References

1 See Appendix A
2. "Determination of Pesticides and
PCBs in Industrial and Municipal
Wastewaters." Report for EPA
Contract 68-03-2606. In preparation.
3. ASTM Annual Book of Standards,
Part 31, D3694. "Standard Practice
for Preparation of Sample Containers
and for Preservation," American
Society for Testing and Materials,
Philadelphia, PA, p. 67S, 1980.
4. Giam, D.S., Chan  H.S. and Nef,
G.S., "Sensitive Method for
Determination of Phthalate Ester
Plasticizers in Open-Ocean Biota
Samples," Analytical Chemistry, 47,
 2225, (1975).
 5. Giam, C.S., Chan, H.S., "Control of
 Blanks in the Analysis of Phthslates in
 Air and Ocean Biota Samples," U.S.
 National Bureau of Standards. Special
 Publication 442, pp.  701-708, 1976.
 6. "Carcinogens-Working With
 Carcinogens," Department of Health,
 Education, and Welfare, Public Health
 Service, Center for Disease Control,
 National Institute for Occupational
 Safety and Health. Publication No.
 77-206, Aug. 1977.
 7. "OSHA Safety and Health
 Standards, General Industry," (29 CFR
  1 91 0), Occupational Safety and
 Health Administration, OSHA 2206,
 (Revised, January 1976).
 8. "Safety in Academic Chemistry
 Laboratories," American Chemical
  Society Publication,  Committee  on
  Chemical Safety, 3rd Edition, 1 979.
  9. Mills, P.A., "Variation of  Florisil
  Activity:  Simple Method for Measuring
  Absorbent Capacity and Its Use in
  Standardizing Florisil Columns,"
  Journal of the Association of Official
  Analytical Chemists, 51, 29 H968I.
  10. "Handbook for AnalyticafQuality
  Control in Water and Wastewatei
  Laboratories," EPA-600/4-79-01 9,
  U.S. Environmental Protection Agency,
  Environmental Monitoring and Support
  Laboratory, Cincinnati, Ohio 45268,
  March 1979.
  11. ASTM Annual Book of Standards,
  Part 31,  D3370,  "Standard Practice
  for Sampling Water," American
  Society for Testing and Materials,
  Philadelphia, PA. p.  76, 1980.
  1 2. "Methods 330.4 (Titrimetric,
  DPD-FAS) and 330.5 (Spectrophoto-
  metric, DPD) for Chlorine, Total
  Residual," Methods for Chemical
  Analysis of Water and Wastes,  EPA
  600-4/79-020, U.S. Environmental
  Protection Agency, Environmental
  Monitoring and Support Laboratory,
  Cincinnati, Ohio 45268, March 1979.
1 3. Goerlitz, D.F. and Law, L.M.,
Bulletin for Environmental
Contamination and Toxicology, 6 9
(1971).
14. "Manual of Analytical Methods for
the Analysis of Pesticides in Human
Environmental Samples," U.S. Environ-
mental Protection Agency,  Health
Effects Research Laboratory, Research
Triangle Park, N.C., EPA Report
600/8-80-038, Section 1 1,B, p.6.
 1 5. Burke, J.A., "Gas Chromatography
for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the
Association of Official Analytical
 Chemists, 48, 1037(1965).
 16. Webb, R.G., and McCall, A.C.,
 "Quantitative PCB Standards for
 Electron Capture Gas
 Chromatography," Journal of
 Chromatographic Science, 11, 366
 (1973).
 1 7. "Method Detection Limit and
 Analytical Curve Studies, EPA Methods
 606, 607, and 608," Special letter
 report for EPA Contract 68-03-2606.
 Environmental Monitoring  and Support
 Laboratory-Cincinnati, Ohio 45268.
                                        608-7
                                                                   July 1982

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Table 1. Chrom
Detect
Parameter
o-BHC
y-BHC
P-BHC
Heptachlor
6-BHC
Aldrin
Hepachlor epoxide
Endosulfan 1
4,4 '-DDE
Dieldrin
Endrin
4,4 '-ODD
Endosulfan II
4,4 '-DDT
Endrin aldehyde
Endosulfan sulfate
Chlordane
Toxaphene
PCB-1016
PCB-1221
PCB- 1232
PCB-1242
PCB- 1248
PCB- 1254
PCB- 12 60
atographic Conditions ar
ion Limits
Retention Time
(min.) r
Column 1
1.35
.70
1.90
2.00
2.15
2.40
3.50
4.50
5.13
5.45
6.55
7.83
8.00
9.40
11.82
14.22
mr
mr
mr
mr
mr
mr
mr
mr
mr
Column 2
1.82
2.13
1.97
3.35
2.20
4.10
5.00
6.20
7.15
7.23
8.10
9.08
8.28
11.75
9.30
10.70
mr
mr
mr
mr
mr
mr
mr
mr
mr
td Method
Method
Detection Limit
W/L
0.003
0.004
0.006
0.003
0.009
0.004
0.083
0.014
0.004
0.002
0.006
0.01 1
0. 004
0.012
0. 023
0.066
0.014
0.24
nd
nd
nd
0.065
nd
nd
nd
 Column 1 conditions: Supelcoport (100/120 mesh) coated
  with 1.5%SP-2250/1.95%SP-2401packedina 1.8m
  long x 4 mm ID glass column with 5% Methane/95%
  Argon carrier gas at a flow rate of 60 mL/min. Column
  temperature isothermal at 200 °C, except for PCB-1016
  through  PCB-1248,  which  should  be  measured  at

 Column 2 conditions: Supelcoport (100/120 mesh) coated
  with 3% 0V-1 in a 1.8m long x 4 mm ID glass column
  with 5 % Methane/95% Argon carrier gas at a flow rate of
  60 mL/min. Column temperature, isothermal at 200 °C
  for  the pesticides;  140°C for PCB-1221  and  1232-
  1 70 °C for PCB-1016 and 1242 to 1268.
mr -  Multiple peak response. See Figures 2  thru  10.
nd — Not determined.
                                                          Table 2.    Distribution of Chlorinated Pesticides and PCBs
                                                                     into Florisil Column Fractions2

                                                                                      Percent Recovery
                                                                                         by Fraction
Parameter
Aldrin
a-BHC
0-BHC
6-BHC
Y-BHC
Chlordane
4,4'-DDD
4, 4 '-DDE
4, 4 '-DDT
Dieldrin
Endosulfan 1
Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB- 1232
PCB-1242
PCB- 1248
PCB- 12 54
PCB- 1260
Fraction
1
100
100
97
98
100
100
99
98
100
0
37
0
0
4
0
100
100
96
97
97
95
97
103
90
95
Fraction
2









100
64
7
0
96
68





4




Fraction
3











91
106

26










Fraction 1-6% ethyl ether in hexane
Fraction 2-15% ethyl ether in hexane
Fraction 3- 50% ethyl ether in hexane
                                   608-6
                                                             July 1982

-------
Table 3.     Single Operator Accuracy and Precision


Parameter
_ 	 _— — —
Aldrin
o-BHC
P-BHC
6-BHC
rBHC
I v
Chlorane
4-4 '-ODD
4, 4' -DDE
4, 4 '-DDT
Dieldrin
Endosulfan 1
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Average
Percent
Recovery
— — —
89
89
88
86
97
93
92
89
92
95
96
97
99
95
87
88
93
95
94
96
88
92
90
92
91
Standard
Deviation
%
2.5
2.0
1.3
3.4
3.3
4. 1
1.9
2.2
3.2
2.8
2.9
2.4
4.1
2. 1
2.1
3.3
1.4
3.8
1.8
4.2
2.4
2.0
1.6
3.3
5.5
Spike
Range
(W/U
•.MI i ~
2.0
/f\
.0
2f*
.0
2.0
;f\ •
.0
20
6.0
3r\
.0
8.0
3 A
.0
3.0
5.0
15
5f\
.O
12
/f\
.0
2.0
200
25
55-110
1 10
28-56
40
40
80
	
                                                     Number
                                                       of
                                                    Analyses
                                                    .•i   in
                                                       15
                                                       15
                                                       15
                                                       15
                                                       15
                                                       21
                                                       15
                                                        15
                                                        15
                                                        15
                                                        12
                                                        14
                                                        15
                                                        12
                                                        11
                                                        12
                                                        15
                                                        18
                                                        12
                                                        12
                                                        12
                                                        12
                                                        12
                                                        18
                                                        18
     Column: 1.5% SP-2250+
             1.95% SP-2401  on Supelcoport
     Temperature: 200°C.
     Detector: Electron capture
0	4         8         12        16
           Retention time, minutes
Figure 1.  Gas chromatogrem of pesticides.

                                    608-9
                                                            Matrix
                                                            Types
                                                                	
                                                              3
                                                              3
                                                              3
                                                              3
                                                              3
                                                              4
                                                              3
                                                              3
                                                              3
                                                              2
                                                              2
                                                              3
                                                              3
                                                               2
                                                               2
                                                               2
                                                               3
                                                               3
                                                               2
                                                               2
                                                               2
                                                               2
                                                               2
                                                                3
                                                                3
Column:  1.5%SP-2250+
         1.95% SP-2401 on
         Supelcoport
Temperature: 200°C.
Detector: Electron capture
       4       8      12
       Retention time, minutes
Figure 2.  Gas chromatogram
          of chlordane.
16
                                                                 July 1982

-------
                       Column:  1.5% SP-2250-
                               1.95% SP-2401 on
                               Supelcopon
                       Temperature: 200°C.
                       Detector: Electron capture
           6      10     14     18     22
                 Retention time, minutes

 Figure 3.  Gas chromatogram of toxaphene.
    Column: 1.5% SP-2250* 1.95% SP-2401 on
           Supelcopon
    Temperature: 160°C.
    Detector: Electron capture
 26
    2       6      10      14      18
             Retention time, minutes

Figure 4.   Gas chromatogram of PCB-1016.

                                   608-10
22
                    Column: 1.5% SP-2250* 1.95% SP-2401 on
                            Supelcopon
                    Temperature: 160°C.
                   Detector: Electron capture
                           -L.
                           6       10      14      18
                             Retention time, minutes
     22
                                                           Figure 6.  Gas chromatogram of PCB-1221.
                 Column: 1.5% SP-2250* 1.95% SP-2401 on
                         Supelcopon
                 Temperature: 160°C.
                 Detector: Electron capture
                 2      6      10      14      18
                           Retention time, minutes

             Figure 6.  Gas chromatogram of PCB-1232.

                  July 1982
22
24

-------
 Column:  1.5% SP-2250+ 1.95% SP-2401 on
          Supelcoport
  Temperature: 160°C.
  Detector: Electron capture
   26      10       14     18
             Retention time, minutes

Figure 7.  Gas chromatogram of PCB-1242.
22
                Column:  1.5% SP-2250+ 1.95% SP-2401 on
                        Supelcoport
                Temperature: 200°C.
                Detector: Electron capture
                                              .1    t
                                                            2         6       10        14       18
                                                                       Retention time, minutes

                                                        Figure 9.  Gas chromatogram of PCB-1254.
                                                              22
  Column:  1.5% SP-2250+ 1.95% SP-2401 on
           Supelcoport
   Temperature: 160°C.
   Detector: Electron capture
    2      6      10     14 ,    18     22
             Retention time, minutes

 Figur* 8.  Gas chromatcgram of PCB-1248.

                                     608-11
                 Column:  1.5% SP-2250+ 1.95% SP-2401 on
                          Supelcoport
                 Temperature: 200°C.
                 Detector: Electron capture
                   2     6      10     14      18    22
                               Retention time,  minutes
               Figure 10.  Gas chromatogram of PCB-1260.
26
                     July 1982
                                       U.S GOVERNMENT PRINTING OFFICE: 19M 759- 102/09-H

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                              METHOD T06                   Revision 1.0
                                                           September, 1986
                 METHOD FOR  THE  DETERMINATION OF PHOSGENE
       IN AMBIENT AIR  USING  HIGH  PERFORMANCE LIQUID CHROMATOGRAPHY
1.    Scope

     1.1   This document describes  a method  for  determination  of
           phosgene in ambient air, in which phosgene  is  collected  by
           passage of the air through a solution of aniline, forming
           carbanilide.  The carbanilide is  determined by HPLC.   The method
           can be used to detect phosgene at the 0.1 ppbv level.
     1.2   Precision for phosgene spiked into a  clean  air stream is
           ^15-20% relative standard deviation.   Recovery is  quantita-
           tive within that precision, down  to less than  3 ppbv.  This
           method has been developed and tested  by a single
           laboratory(D, and, consequently, each laboratory  desiring
           to use the method should acquire sufficient precision
           and recovery data to verify performance under those
           particular conditions.  This method is more sensitive,
           and probably more selective, than the standard colorimetric
           procedure  currently  in widespread use for workplace monitor-
           1ng(2).

 2.    Applicable  Documents

      2.1  ASTM  Standards

           D1356 - Definitions  of  Terms  Related  to Atmospheric  Sampling
           and Analysis(3).

      2.2  Other Documents

            Standard NIOSH Procedure for Phosgene(2).
            U.S. EPA Technical Assistance Document^).

-------
                                   T06-2
 3.   Summary of Method

      3.1   Ambient air is drawn through a midget impinger containing
            10 ml of 2/98 aniline/toluene (by  volume).   Phosgene
            readily reacts with  aniline  to form  carbanilide  (1,3-
            diphenylurea), which is  stable indefinitely.
      3.2   After sampling,  the  impinger contents are transferred to
            a  screw-capped vial  having a Teflon-lined cap  and
            returned  to the  laboratory for analysis.
      3.3   The  solution  is  taken to dryness by  heating to 60°C on an
            aluminum  heating block under  a  gentle stream of pure
            nitrogen  gas.  The residue is dissolved in 1 mL of
            acetonitrile.
      3.4    Carbanilide is determined in the acetonitrile solution
            using reverse-phase HPLC with an ultraviolet absorbance
            (UV) detector operating at 254 nm.

4.   Significance

     4.1   Phosgene is widely  used  in  industrial operations,  primarily
           in  the synthetic  organic  chemicals  industry.   In  addition,
           phosgene is produced  by  photochemical  degradation  of
           chlorinated hydrocarbons  (e.g., trichloroethylene) emitted
           from  various sources.  Although phosgene is  acutely
           toxic, its effects  at  low levels (i.e., 1 ppbv  and below)
           are unknown.   Nonetheless, its  emission into and/or
           formation  in ambient  air is of  potential concern.
     4.2   The conventional  method for phosgene  has utilized a
           colorimetric procedure involving reaction with
           4,4'-nitrobenzyl pyridine in  diethyl phthalate.  This
           method cannot detect phosgene  levels below   10 ppbv and
           is  subject to numerous interferences.   The method described
           herein is  more sensitive (0.1 ppbv detection limit) and
           is believed to be more selective due to the chromatographic
           separation step.  However, the method  needs  to be more
           rigorously tested for interferences  before its degree
          of selectivity can be firmly established.

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                                  T06-3
5.   Definitions

           Definitions used in this document and  in any user-prepared
         •  SOPs should be consistent with ASTM D1356 (3).   All
           abbreviations and symbols are defined  within this
           document at the point of use.

6.   Interferences

     6.1   There are very few interferences in the method, although
           this aspect of the method needs to be more thoroughly
           investigated.  Ambient levels of nitrogen oxides, ozone,
           water vapor, and S02  are known not to interfere.  Chloroformates
           can  cause  interferences  by reacting with the aniline to form
           urea, which produces a peak  that overlies the carbanilide
           peak in the HPLC trace.   Presence  of chloroformates should be
           documented before  use of this method.   However, the inclusion
           of  a HPLC  step  overcomes most potential  interferences  from
           other organic  compounds. High  concentrations of  acidic materials
           can cause  precipitation  of aniline salts in  the  impinger, thus
           reducing the  amount  of  available  reagent.
      6.2  Purity  of  the aniline reagent  is  a critical  factor, since
           traces  of  carbanilide have been found  in reagent-grade
           aniline.   This problem  can be  overcome by vacuum distil-
            lation  of  aniline in an all-glass apparatus.

 7.   Apparatus

      7.1   Isocratic  high performance liquid chromatography (HPLC)
            system consisting of a  mobile-phase reservoir, a high-pressure
            pump,  an injection valve, a  Zorbax ODS or C-18 reverse-phase
            column, or equivalent (25 cm x 4.6 mm ID), a variable-wavelength
            UV  detector operating at 254 nm, and a data system or strip-
            chart recorder (Figure  1).
      7.2   Sampling system - capable of accurately and precisely
            sampling  100-1000 mL/minute of ambient  air  (Figure 2).

-------
                                   T06-4

      7.3   Stopwatch.
      7.4   Friction-top metal  can, e.g.,  one-gallon (paint  can)  -  to
            hold sampling reagent  and samples.
      7.5   Thermometer - to record ambient  temperature.
      7.6   Barometer (optional).
      7.7   Analytical  balance  - 0.1  mg  sensitivity.
      7.8   Midget  impingers -  jet  inlet type,  25 ml.
      7.9   Nitrogen  evaporator with  heating block  -  for concentrating
            samples.
      7.10   Suction filtration  apparatus - for  filtering HPLC
            mobile phase.
      7.11   Volumetric  flasks - 100 ml and 500 mL.
      7.12   Pipettes  -  various  sizes, 1-10 ml.
      7.13   Helium purge  line (optional) - for degassing HPLC
            mobile phase.
      7.14   Erlenmeyer  flask, 1-L - for preparing HPLC mobile
            phase.
      7.15   Graduated cylinder,  1 L - for preparing  HPLC mobile
           phase.
      7.16  Microliter syringe,  10-25 uL -  for HPLC  injection.

8.   Reagents and Materials

     8.1   Bottles,  16 02. glass,  with  Teflon-lined screw  cap  -  for
           storing  sampling reagent.
     8.2   Vials, 20  mL, with Teflon-lined screw cap -  for holding
           samples  and extracts.
     8.3   Granular charcoal.
     8.4   Acetonitrile,  toluene, and methanol  - distilled in  glass
           or pesticide grade.
     8.5   Aniline -  99+%,  gold label from Aldrich  Chemical  Co.,  or
           equivalent.

-------
                                 T06-5

     8.6    Carbanilide  -  highest  purity  available; Aldrich Chemical
           Co.,  or  equivalent.
     8.7    Nitrogen,  compressed gas  cylinder  -  99.99%  purity  for
           sample evaporation.
     8.8    Polyester  filters,  0.22  urn -  Nuclepore, or  equiv.

9.   Preparation of Sampling Reagent

     9.1    Sampling reagent is prepared  by placing  5.0 ml of  aniline in
           a 250-mL volumetric flask and diluting to the mark with  toluene,
           The flask  is inverted  10-20 times  to mix  the reagent.   The
           reagent is then placed in a clear  16-ounce  bottle  with a
           Teflon-lined screw cap.   The reagent is refrigerated until use.
     9.2   Before use, each batch of reagent  is checked for purity by
           analyzing  a 10-mL portion according to the  procedure described
           in Section 11.  If acceptable purity (<50 ng of carbanilide
           per 10 ml of reagent)  is not obtained, the aniline or toluene
           is probably contaminated.

 10.  Sampling

     10.1  The  sampling apparatus is assembled and should be similar
           to that shown  in Figure  2.   EPA Method 6 uses essentially
           the  same  sampling system (5).   All glassware (e.g.,
           impingers,  sampling bottles, etc.)  must be thoroughly
           rinsed with methanol  and oven-dried before use.
     10.2  Before  sample  collection, the  entire  assembly (including
           empty sample  impingers)  is installed  and the flow rate
           checked at  a  value near  the  desired rate.  Flow rates
            greater than  1000  mL/minute  (^2%)  should not be used  because
            impinger  collection efficiency may  decrease. Generally,
            calibration is accomplished  using  a soap bubble flow

-------
                              T06-6

       meter or calibrated wet test meter  connected to  the  flow
       exit, assuming that the entire  system  is  sealed.  ASTM Method
       D3686 describes an  appropriate  calibration  scheme that does
       not require a  sealed-flow  system downstream of the pump (3).
 10.3  Ideally,  a  dry gas  meter is  included in the system to record
       total  flow, if the  flow rate  is sufficient  for its use.
       If a dry  gas meter  is  not  available, the  operator must measure
       and record  the sampling flow  rate at the  beginning and end of
       the sampling period  to  determine sample volume.  If the
       sampling  time  exceeds  two  hours, the flow rate should be
       measured  at intermediate points during the sampling period.
       Ideally,  a  rotameter should be included to allow observation of
       the flow  rate  without  interruption of the sampling process.
 10.4   To  collect  an  air sample, the midget impingers  are
       loaded with 10 ml each of sampling reagent.   The impingers
       are  installed  in the sampling system and sample flow is
       started.  The  following parameters are recorded on the
       data sheet  (see Figure 3 for an  example):   date,  sampling
       location, time, ambient temperature, barometric pressure
       (if available), relative humidity  (if available), dry
      gas meter reading (if appropriate),  flow rate,  rotameter
      setting, sampling reagent batch  number, and  dry gas  meter
      and pump identification numbers.
10.5  The sampler  is  allowed  to operate  for the  desired period,
      with periodic recording of  the variables  listed above.
      The total  flow  should not exceed 50  L.   If it does, the
      operator must use a  second  impinger.
10.6  At the end of the sampling  period, the  parameters  listed
      in Section 10.4 are  recorded  and the  sample  flow  is stopped.
      If a dry gas meter is not used, the  flow rate must be checked
      at the end of the sampling  interval.  If the flow rates at the
      beginning  and end of  the sampling period differ by more than
      15%, the sample should  be marked as  suspect.

-------
                            T06-7
 10.7  Immediately after sampling, the impinge r is removed from
      the  sampling  system.  The contents of the impinger are
      emptied  into  a  clean 20-mL glass vial with a Teflon-
     ' lined  screw cap.  The impinger is then rinsed with
      2-3  ml of  toluene and the rinse solution is added to the
      vial.  The vial  is  then  capped, sealed with Teflon tape,
      and  placed in a friction-top  can containing 1-2  inches
      of granular charcoal.  The samples are stored in the
      can  and  refrigerated until analysis.
10.8  If a dry gas  meter  or  equivalent total flow indicator
      is not used,  the average sample  flow rate must  be  calculated
      according to  the following equation:
                       Q! +  Q2 •••• QN
                  QA

      where
Q2
      Q/\ = average flow rate (mL/minute).
      QN = flow rates determined at the beginning, end,
           and intermediate points during sampling.
       N = number of points averaged.
 10.9  The total flow is then calculated using the following
      equation:
                   Vm =
                           (T2-Ti)QA
                              1000
        where
                   Vm  =  total  sample  volume  (L)  at measured
                        temperature and  pressure.
                   T2  =  stop  time.
                   TI  =  start time.
                  -T2  =  total  sampling time  (minutes).
                   Qa  =  average flow  rate (mL/minute).

-------
                                  T06-8
11.  Sample Analysis

     11.1   Sample  Preparation
           11.1.1  The  samples are  returned to the laboratory in 20-ml
                  screw-capped vials and refrigerated in charcoal
                  containing cans  until analysis.
           11.1.2  The  sample vial  is placed in an aluminum
                  heating block maintained at 60°C and a gentle
                  stream of pure nitrogen gas is directed
                  across the sample.
          11.1.3  When the sample reaches complete dryness,  the vial
                  is removed from the heating block,  capped, and
                 cooled to near room temperature.  A 1-mL volume
                 of HPLC mobile  phase (50/50 acetonitrile/water)
                 is placed in the  vial.  The vial  is  then capped
                 and gently shaken to  dissolve  the residue.
          11.1.4 The concentrated  sample  is  then refrigerated
                 until  HPLC analysis,  as described in Section  11.2.

    11.2   HPLC Analysis
          11.2.1 The HPLC  system is  assembled and calibrated as described in
                Section 12.  The  operating parameters are as  follows:
                             Column:   C-18 RP
                       Mobile Phase:   30% acetonitrile/70%  distilled water
                           Detector:   ultraviolet, operating at 254 nm
                          Flow Rate:   1 mL/min
                Before each analysis, the detector baseline is checked
                to ensure stable operation.
         11.2.2 A 25-uL aliquot  of the sample,  dissolved in HPLC
                mobile phase,  is drawn into  a clean  HPLC injection
                syringe.  The sample injection  loop  is  loaded  and
                an injection is  made.   The data system  is activated
                simultaneously with  the injection and the point  of
                injection  is marked  on the strip-chart  recorder.

-------
                                T06-9
          11.2.3 After approximately one minute, the injection valve
                is  returned to the "load" position and the syringe and
                valve are  flushed with mobile phase in preparation
                for the  next sample analysis.
          11.2.4 After elution of carbanilide, data acquisition is
                terminated and the component concentrations are
                calculated as described  in  Section 13.
          11.2.5 Once  a  stable baseline  is achieved, the  system can be
                used  for further  sample  analyses  as described above.
          11.2.6  If the  concentration  of  carbanilide exceeds the
                 linear  range  of  the  instruments,  the  sample should
                 be diluted with  mobile  phase,  or  a smaller  volume
                 can be  injected  into  the HPLC.
          11.2.7 If the  retention  time is not duplicated, as determined
                 by the calibration curve, you may increase  or decrease
                 the acetonitrile/water ratio to obtain the  correct  elution
                 time, as  specified in Figure 4.  If  the elution  time is too
                 long, increase the ratio; if it is too short, decrease  the
                 ratio.
          11.2.8 If a dirty column causes improper detection of carbanilide,
                 you may reactivate the column by reverse solvent flushing
                 utilizing the following sequence: water, methanol,
                 acetonitrile, dichloromethane, hexane, acetonitrile,
                 then 50/50, acetonitrile  in water.
12.  HPLC Assembly  and Calibration
     12.1  The HPLC system  is  assembled  and  operated according to the
           parameters  outlined in  Section  11.2.1.  An  example  of  a typical
           chromatogram  oabtained  using  the  above  parameters  is shown  in
           Figure  4.
     12.2  The mobile  phase is prepared  by mixing  500  mL  of  acetonitrile
           and 500 mL  of reagent  water.   This mixture  is  filtered
           through  a 0.22-um polyester membrane filter in an all-glass
           and Teflon  suction  filtration.  A constant  back pressure
           restrictor (50  psi) or short length (6-12  inches) of 0.01-inch
           I.D. Teflon tubing should  be placed after  the detector to
           eliminate further mobile phase outclassing.

-------
                               T06-10
  12.3  The mobile phase is placed  in the  HPLC  solvent  reservoir  and
        the pump is set  at  a flow rate of  1 mL/minute and  allowed to
        pump for 20-30 minutes  before the  first analysis.  The detector
        is  switched on at least  30  minutes before the first analysis
        and the  detector output  is  displayed on a strip-chart recorder
        or  similar output device  at a  sensitivity of ca 0.008 absorbance
        units full  scale (AUFS).  Once a stable baseline is achieved,
        the  system  is ready, for calibration.
 12.4   Carbanilide standards are prepared in HPLC mobile phase.
       A concentrated stock solution of  100 mg/L is prepared by
       dissolving 10 mg of carbanilide in 100 ml  of mobile phase.
       This solution is used to prepare calibration standards
       containing concentrations of 0.05-5 mg/L.
 12.5  Each calibration  standard (at  least five levels) is analyzed
       three times and  area response  is tabulated  against  mass injected.
       All  calibration  runs are performed  as  described  for sample
       analyses  in Section  11.   Using the  UV  detector,  a linear
       response  range  (Figures  5a through  5e) of approximately 0.1  to
       10 mg/L should be achieved for a  25-uL injection volumes.  The
       results may be used  to prepare  a  calibration curve, as illus-
       trated in Figure 6.   Linear  response is  indicated where a  corre-
       lation coefficient of at  least  0.999 for a linear least-squares
       fit  of the  data (concentration  versus area response) is obtained.
12.6   Once  linear  response has been documented, an intermediate
       concentration standard near the anticipated levels for ambient
       air, but  at  least 10 times the detection  limit, should be
       chosen for daily calibration.  The response for carbanilide
       should be within 10% day to day.  If greater variability  is
       observed,  more frequent calibration may be  required  to ensure
      that  valid results are obtained  or a  new calibration  curve
      must  be developed  from fresh  standards.
12.7  The  response for  carbanilide  in the  daily calibration  standard
      is used to calculate  a response factor  according  to  the following
      equation:

-------
          where
                      RFC =
                                 T06-11
                               Cc X Vj
                                   RC
                 RFC = response factor (usually area counts) for
                       carbanilide  in nanograms injected/response
                       unit.
                 Cc  = concentration  (mg/L) of carbanilide  in the
                       daily calibration  standard.
                 Vi  = volume  (uL)  of calibration standard  injected
                 Rc  = response  (area counts)  for carbanilide in
                       calibration  standard.
13.  Calculations

     13.1  The volume of air sampled is often reported  unconnected  for
           atmospheric conditions (i.e., under ambient  conditions).
           The value should be adjusted to standard conditions
           (25°C and 760 mm pressure) using the following equation:
           where
                       Vs ' Vm
298
                                 760   273 + TA
                  Vs = total sample volume (L) at 25°C and 760 mm Hg
                       pressure.
                  Vm = total sample volume (L) under ambient conditions,
                       calculated as in Section 10.9 or from dry gas
                       meter reading.
                  PA = ambient  pressure (mm Hg).
                  TA = ambient  temperature (°C).

-------
                             T06-12
13.2  The concentration of carbanilide is calculated  for each
      sample using the following  equation:
                  Wd  = RFC  X  Rd  X J
                                    V

                                    VI

       where

              Wd  = total quantity of carbanilide (ug) in the sample,
              RFC = response factor calculated in Section 12.7.
              Rd  = response (area counts or other response units)
                    for carbanilide in sample extract.
              VE  = final volume (mL)  of sample extract.
              Vj  = volume (uL)  of extract  injected  into  the HPLC
                    system.
 13.3  The concentration  of  phosgene in  the original  sample is
       calculated  from  the following equation:

                   C. •     "d       99
                    A   Vm (or vs)  " In "  100°
       where

             CA =  concentration of  phosgene  (ng/L)in the original
                  sample.
             Wd = total quantity of carbanilide (ug) in sample.
             Vm = total sample volume (L) under ambient conditions.
             Vc = total sample volume (L) at 25 °C and 760 mm Hg.
            _99 = the molecular weights (g/mole) of  phosgene and
            212   carbanilide are 99 and 212 g/mole, respectively.

13.4  The phosgene concentrations  can  be converted to ppbv using the
      following equation:

-------
                           T06-13
                                  /L) x

     where
                      CA (ppbv) - CA (ng/L)  x 244
                      CA  (ng/L) is calculated using Vs-
14   Performance Criteria  and  Quality Assurance
     This section summarizes retired quality  assurance  (QA) measures and
     provides guidance concerning  performance  criteria that  should be
     achieved within each laboratory.
14.1
           Standard Operating Procedures (SOPs)
            14.L1  Users  should  generate SOPs describing ^*"<«"
                   activities  in their  laboratory:  1) assembly, calibra
                   tion,  and operation  of  the  sampling system with make
                   and model of  equipment  used;  2)  preparation, purifica-
                   tion,  storage,  and handling of sampling  reagent  and
                   samples; 3) assembly, calibration, and  operation of
                   the HPLC system with make and model  of  equipment used;
                   and 4)  all aspects of data recording and process! ng.
                   including  lists of computer hardware and software used,

             14 l 2 SOPs  should  provide  specific  stepwise instructions
                    and should be  readily  available to and  understood
                    by the laboratory personnel  conducting  the work.

       14.2  HPLC  System Performance

             14  2.1 The  general appearance of the HPLC chromatogram
                    should be similar to that illustrated  in Figure 4.
              14 2 2 The  HPLC  system  efficiency  and peak asymmetry
                '    factor should be determined  in the  following manner:

-------
                              T06-14

              A solution of carbanilide corresponding to at
              least 20 times the detection limit should be
              Injected with the recorder chart sensitivity
              and speed set to yield a peak approximately
              75% of full scale and 1 cm wide at half height.
              The peak asymmetry factor is determined as shown
              in Figure 7,.and should be between 0.8 and 1.8.
       14.2.3 HPLC system efficiency is calculated  according to
              the following equation:

                   N = 5.54   tr
                            Wl/2
              where

                      N     = column  efficiency  (theoretical plates).
                      tr    = retention time (seconds) of carbanilide.
                      Wl/2  = width of component peak at half
                            height  (seconds).
             A column efficiency of >5,000 theoretical plates
             should be obtained.
      14.2.4 Precision of  response for replicate HPLC injections
             should be +10% or less, day to day, for calibration
             standards.  Precision of retention times should be +2%.
             on  a given day.

14.3  Process Blanks

      14.3.1  Before use,  a  10-mL aliquot  of each  batch  of  sampling
             reagent should be analyzed  as  described in  Section 11.
             The  blank should  contain  less  than  50  ng  of   carbanilide
             per  10-mL aliquot.

-------
                            T06-15
     14.3.2 At least one field blank or 10% of the field samples,
            whichever is larger, should be shipped and analyzed
            with each group of samples.  The field blank is treated
         .   identically to the samples except that no air is drawn
            through the reagent.  The same performance criteria
            described in Section  14.3.1 should be met for process
            blanks.

14.4  Method Precision and  Recovery

      14.4.1 Analysis  of  replicate samples indicates  that  a  precision
             of +15-20%  relative standard  deviation can  be readily
             achieved  (see Table 1).  Each laboratory should collect
             parallel  samples periodically (at least  one for each
             batch of samples) to document its precision in conduct-
             ing the method.
      14.4.2 Precision for replicate HPLC injections  should be +10%
             or better, day to day, for calibration standards.
      14.4.3 Before using the method in the field, each laboratory
             must  confirm the performance of the method under its
             particular conditions.  Since static, dilute,  gas phase
             standards of  phosgene  are  unstable, a dynamic  flow/
              permeation tub  system  should be  assembled  as described
              in the literature^).  ASTM  Method  D 3609(3)  should  be
              used as  the  protocol for  operating  such a  system.
       14.4.4 Once a suitable dynamic  flow/permeation tube system
              has been constructed, a  series  of three samples from
              the outlet gas stream (60 L) should be  sampled at three
              different spike levels (achieved by adjusting the air
              flow through the permeation chamber).   Precision and
              recovery data comparable to those shown in Table 1
              should be achieved.

-------
                                   T06-16



                                 REFERENCES

4'
5-

-------
                       INJECTION
                        VALVE
                                      COLUMN
                                           VARIABLE
                                          WAVELENGTH
                                              UV
                                           DETECTOR
   DATA
  SYSTEM
 MOBILE
 PHASE
RESERVOIR
STRIPCHART
 RECORDER
                     FIGURE 1. TYPICAL HPLC SYSTEM

-------
                                           SILICA GEL
                   ROTAMETER
VENT
 DRY
 TEST
METER
                                PUMP
                                                                SAMPLE
                                                               IMPINGERS
                                                              7
mm
* '
• 1



L


r
|
*'-<
-
f
L**
                                                                 Lr
                                                              V
                                                           M
                                                                       7.
                                                            10 ml of 2/98
                                                            Aniline/Toluene
                                                                     FLOW
                                                                  o
                                                                  
-------
                                     T06-19

                              .SAMPLING DATA SHEET
                            (One Sample per Data  Sheet)
PROJECT:

SITE:
                                              DATES(S) SAMPLED:
LOCATION:
TIME  PERIOD SAMPLED:

OPERATOR: 	
INSTRUMENT MODEL NO:

PUMP SERIAL NO: 	

SAMPLING  DATA
                                              CALIBRATED BY:
                      Sample Number:

                 Start Time: _______
  Stop Time:
Time
1

•
•3
4
N.
Dry Gas
Meter
Reading





Rotameter
Reading





Flow
Rate,*Q
mL/min





Ambient
Temperature
°C





Barometric
Pressure,
mm Hg





Relative
Humidity, %
.. «^_^_ M—^— »^— «» ™ '"





Comments



.-Mil 1 •' ™'™
• HI—I II. ........
    Total Volume Data1
       Vm = (Final  -  Initial) Dry  Gas Meter Reading, or
                    Q   '" Q
                             x     	1
                               1000 x (Sampling Time in Minutes)
                            L



                            L
     * Flow rate from rotameter or soap bubble calibrator
       (specify which).
    ** Use data from dry  gas meter if  available.
                   FIGURE 3. TYPICAL SAMPLING DATA FORM

-------
                               T06-20
             \D
              •
             ro
     f
    o
    UJ
                                              OPERATING PARAMETERS
                                                      HPLC
                                  Column: C-18 RP
                                  Mobile Phase: 30% Acetonitrile/70% Distilled Water
                                  Detector: Ultra violet operating at 254 nm
                                  Flow Rate: 1  ml/min
                                  Retention Time: 3.59 minutes
                                 AUG. 22. 1986  15:25:17  CHART 0.50 CM/MIN
                                                 RUN #50   CALC *0
                                 COLUMN           SOLVENT  OPR ID:
                                 EXTERNAL STANDARD QUANTITATION

                                 PEAK*    AMOUNT  RT   EXP RT
                                         2.7530O   2.74
                                      10020.20000   3.59
                                 TOTAL  1002300000
  AREA
   2753 L
10020345 L
    RF
OOOOOOOEO
O.OOOOOOEO
FIGURE 4. CHROMATOGRAM FOR 3  ppbv OF
             PHOSGENE SPIKED INTO CLEAN AIR

-------
                                   3.59
          OPERATING PARAMETERS
                HPLC

Column: C-18 RP
Mobile Phase: 30% Acetonitrile/70% Distilled Water
Detector: Ultra violet operating at 254 nm
Flow Rate: 1 ml/min
Retention Time: 3.59 minutes
                       (a)
                                                   3.55
       (b)
                                                    3.57
    (C)
                                  TIME-
                               o
                               UJ
                               -3
                               o
                               UJ
                                  TIME-
            o
            UJ
            -3
            z
 TIME
  3/iQ
      CONG
       2/tg
       5/tg
  AREA
COUNTS
 2126577
 4243289
 6312128
 8373790
10020345
                                          3.60
(d)
                                               3.59
(e)
       FIGURE 5a-5e. HPLC CHROMATOGRAM OF
                      VARYING CARBANILIDE CONCENTRATIONS

-------
                   T06-22
                          CORRELATION COEFFICIENT:
                                  0.9999
                    OPERATING PARAMETERS
                            HPLC
       Column: C-18 RP
       Mobile Phase: 30% Acetonitrile/70% Distilled Water
       Detector: Ultra violet operating at 254 nm
       Flow Rate: 1 ml/min
       Retention Time: 3.59 minutes
  2345
     CARBANILIDE
FIGURE 6. CALIBRATION CURVE FOR
          CARBANILINE

-------
                    T06-23
                             BC
              Asymmetry Factor = TJT
              Example Calculation:

               Pea* Height = DE = 100 mm

               10% Peak Height = BD = 10 mm

               Peak Width at 10% Peak Height -

                  AB = 11 mm

                  BC = 12 mm

                                    12
              Therefore: Asymmetry Factor =
AC = 23 mm
FIGURE 7. PEAK ASYMMETRY CALCULATION

-------
                    T06-24
    TABLE 1:  PRECISION AND RECOVERY DATA
              FOR PHOSGENE IN CLEAN AIR
 Phosgene
Concentration,
ppbv
0.034
0.22
3.0
4.3
20
Recovery,
63
87
99
109
99
Standard
Deviation
13
14
3
12
14
   200                 96                   7
======================a==-==-=============-==____.

-------
                                                            Revision 1.0
                                                            September. 1986
                               METHOD T07
          METHOD  FOR  THE  DETERMINATION OF N-NITROSODIMETHYLAMINE
                 IN AMBIENT  AIR USING GAS CHROMATOGRAPHY
1.   Scope

     1.1   This document describes a method for determination  of  N-
           nitrosodimethyl amine (NDMA)  in ambient  air.   Although  the
           method, as described, employs gas chromatography/mass
           spectrometry (GC/MS), other detection systems are allowed.
     1.2   Although additional documentation of the performance of this
           method is required, a detection limit of better than 1 ug/m3
           is achievable  using GC/MS (1,2).  Alternate, selective GC
           detection systems such as a thermal energy analyzer (2), a
           thermionic nitrogen-selective detector (3), or a Hall  Electro-
           lytic conductivity detector  (4) may prove to be more sensitive
           and  selective  in some  instances.

 2.   Applicable Documents

      2.1   ASTM Standards
            D1356 Definitions  of Terms  Related  to  Atmospheric  Sampling
            and Analysis (5)
      2.2   Other Documents
            Ambient air studies (1,2)
            U.S. EPA Technical Assistance Document (6)

 3.   Summary of Method

      3.1   Ambient air is drawn through a Thermosorb/N  adsorbent
            cartridge at  a rate of approximately 2 L per minute for
            an  appropriate period of time.  Breakthrough has been shown

-------
                                    T07-2
             not  to  be  a  problem with  total  sampling  volumes of 300 L
             (i.e.,  150 minutes at  2 L  per minute).   The selection
             of Thermosorb/N absorbent  over  Tenax GC, was due, in part,
             to recent  laboratory studies indicating  artifact formation
             on Tenax from the presence of oxides of  nitrogen in the sample
             matrix.
      3.2    In the  laboratory, the  cartridges are pre-eluted with 5 ml
             of dichloromethane (in the same direction as sample flow)  to
             remove  interferences.   Residual  dichloromethane is removed by
            purging the cartridges with air in the  same direction.   The
            cartridges are then eluted, in  the reverse direction, with 2 ml
            of acetone.  This  eluate is collected in  a screw-capped  vial
            and  refrigerated until  analysis.
      3.3   NDMA  is  determined  by  GC/MS using  a  Carbowax 20M capillary
            column.   NDMA is quantified from the response of the m/e 74
            molecular ion using an  external  standard  calibration method.

 4.    Significance

      4.1    Nitrosamines,  including  NDMA, are  suspected human carcinogens.
            These compounds may be present in  ambient air as a result of
            direct emission (e.g., from tire manufacturing)  or from atmos-
            pheric reactions between secondary or tertiary amines and NOX.
      4.2    Several  papers (1,2,4)  have been published describing analytical
            approaches  for NDMA detennination.  The purpose  of  this  document
            is to combine the attractive features of these methods into
           one standardized method.  At the present time, this method  has
           not been  validated  in  its final  form, and, therefore,  one must
           use caution when employing  it for specific applications.

5.   Definitions

     Definitions  used in  this document and  in  any user-prepared SOPs should
     be  consistent with ASTM 01356(5).   All  abbreviations and  symbols  are
     defined within  this  document  at the point of use.

-------
                                  T07-3
6.   Interferences
     Compounds having retention times similar to  NDMA,  and yielding
     detectable m/e 74 ion fragments, may interfere in  the method.   The
     inclusion of a pre-elution step in  the sample desorption  procedure
     minimizes the number of interferences.  Alternative GC  columns  and
     conditions may be required to overcome interferences in unique
     situations.

7.   Apparatus

     7.1   GC/MS System - capable of temperature-programmed, fused-silica
           capillary column operation.  Unit mass resolution or better to
           300 amu.  Capable of full scan and selected ion monitoring
           with  a  scan rate of 0.8 second/scan or better.
     7.2   Sampling  system - capable of accurately and precisely sampling
           100-2000  mL/minute of  ambient air.  (See Figure 1.)  The dry
           test  meter may not be  accurate at flows below 500 mL/minute;
           in  such cases  it should be replaced by recorded flow readings
           at  the  start,  finish,  and hourly during the collection.  See
           Section 9.4.
     7.3   Stopwatch.
     7.4   Friction  top metal  can, e.g., one-gallon (paint  can) - to  hold
           clean cartridges and samples.
     7.5   Thermometer  -  to record  ambient  temperature.
     7.6   Barometer (o'ptional).
     7.7   Glass syringe  -  5 mL with Luer* fitting.
     7.8   Volumetric flasks -2  mL, 10 mL, and  100 mL.
     7.9   Glass syringe  -  10  uL  for GC injection.

 8.  Reagents and Materials

     8.1    Thermosorb/N - Available from Thermedics  Inc.,  470 Wildwood  St.,
            P.O.Box 2999,  Woburn,  Mass.,  01888-1799,  or equivalent.

-------
                                   T07-4
      8.2   Dichloromethane  -  Pesticide quality, or equivalent.
      8.3   Helium  -  Ultrapure compressed gas  (99.9999%).
      8.4   Perfluorotributylamine  (FC-43) - for GC/MS calibration.
      8.5   Chemical  Standards - NDMA solutions.  Available from various
            chemical  supply  houses.  Caution:  NDMA is a suspected human
            carcinogen.  Handle in accordance with OSHA regulations.
      8.6    Granular  activated charcoal  - for preventing contamination of
            cartridges during storage.
     8.7    Glass jar, 4 oz - to hold cartridges.
     8.8    Glass vial - 1 dram, with Teflon®-lined screw cap.
     8.9    Luer® fittings -  to connect  cartridges  to  sampling system.
     8.10  Acetone- Reagent  grade.

9.   Sampling

     9.1   Cartridges (Thermosorb/N)  are  purchased prepacked  from  Thermedics
           Inc.   These  cartridges are 1.5 cm  ID x  2 cm  long polyethylene
           tubes  with Luer®-type  fittings on each  end.   The adsorbent  is
           held in  place  with  100-mesh stainless steel  screens at  each
           end.   The  cartridges are  used as received and are  discarded
           after  use.  At  least one  cartridge  from each  production lot
           should be  used  as a blank to check  for contamination.   The
           cartridges are  stored in  screw-capped glass jars (with  Luer®
           style  caps), and placed in a charcoal-containing metal  can when
           not in use.
    9.2    The sampling system may employ either a mass flow controller or
           a dry test meter.   (See Figure 1.)   For purposes of discussion,
           the following procedure assumes the use of  a dry test meter.
    9.3    Before sample collection, the entire assembly (including a
           "dummy" sampling cartridge) is installed and the flow rate is
           checked at a  value near the desired  rate.   In general, flow
           rates of 100-2000  mL/minute should  be employed.   The flow rate
          should  be adjusted so that no  more  than  300  L of air is  col-
          lected  over the desired sampling  period. Generally, calibra-
          tion is accomplished using a  soap bubble flow meter or

-------
                            T07-5
      calibrated  wet  test meter connected to the flow exit, assuming
      the system  is sealed.  ASTM Method 3686 describes an
      appropriate calibration  scheme  not requiring a sealed flow
      system downstream of the pump.
9.4   Ideally,  a  dry  gas meter is  included  in the system to record
      total  flow.  If a dry  gas meter is not available, the operator
      must measure and record  the  sampling  flow  rate at the
      beginning and  end of the sampling period to determine sample
      volume.  If the sampling period exceeds two hours, the  flow
      rate should be measured  at  intermediate points during the
      sampling period.  Ideally,  a rotameter should  be included  to
      allow observation of the flow rate without interruption of the
      sampling process.
9.5   To collect an air sample,  a new Thermosorb/N  cartridge  is
      removed from the glass jar and connected  to the  sampling
      system using a  Luer® adapter fitting.  The glass jar is sealed
      for later  use.   The following  parameters  are  recorded on the
      data  sheet (see Figure  2 for an example):   date, sampling
      location,  time, ambient temperature, barometric pressure (if
      available), relative humidity  (if available), dry gas meter
      reading  (if appropriate), flow rate, rotameter setting,
      cartridge  batch number, and dry  gas meter and pump
       identification  numbers.
 9.6   The sampler is allowed  to operate for the desired period,
       with  periodic  recording of the variables  listed above.  The
       total  flow should not exceed  300 L.
 9.7   At the end of  the sampling  period, the parameters listed  in  Section
       9.5 are recorded and  the  sample flow is stopped.  If a dry gas
       meter is not  used,  the  flow rate must be  checked at the end  of
       the sampling  interval.   If  the flow  rates at  the beginning and
       end of the sampling period  differ  by more than  15%, the
       sample should  be marked as  suspect.
 9.8   Immediately after sampling, the cartridge is  removed  from
       the sampling system,  capped, and placed  back  in the 4-oz

-------
                             T07-6
       glass jar.   The jar  is then capped, sealed with Teflon® tape,
       and  placed  in a friction-top can containing 1-2 inches of
       granular charcoal.   The samples are stored in the can until
       analysis.
 9.9    If a dry gas meter or equivalent total flow indicator is not
       used, the average sample flow rate must be calculated
       according to the following equation:
      where
             QA * average flow rate (mL/minute).
 Ql> Q2» ••••ON = fl°w rates determined at beginning,
                  end, and immediate points during
                  sampling.
             N  =  number of points averaged.

9.10  The total  flow is then calculated using  the following
      equation:
                           1000
      where
             Vm  =  total  sample volume  (L) at measured
                  temperature and pressure.
             T£  =  stop time.
             TI  =  start  time.
          T£-TI  =  sampling time  (minutes).

-------
                                 T07-7
     9.11   The total  volume  (Vs) at standard conditions, 25°C and 760
           mm Hg,  is  calculated from the following equation:
                               y  PA  y     298
                       u   _  u   X  H  X
                       vs    m
                                 760    273 + tA
           where   Vs  =  total  sample volume (L) at  standard
                       conditions  of  25° C and 760 mm Hg.
                  Vm  =  total  sample volume (L) at  measured
                       temperature and  pressure.
                  PA  =  average  barometric pressure (mm  Hg).
                  tA  =  average  ambient  temperature (°C).

10.  Sample Desorption

     10.1  Samples are  returned to the  laboratory  and prepared  for
           analysis within one  week of  collection.
     10.2  Using  a glass syringe, the samples  are  pre-eluted  to remove
           potential  interferences by passing  5  mL of dichloromethane
           through the  cartridge, in  the  same  direction as  sample  flow.
           This operation should be conducted  over approximately a  2-minute
           period.  Excess solvent is expelled by  injecting  5  mL  of air
           through the  cartridge, again using  the  glass syringe.
     10.3  The NDMA is  then desorbed  passing  2 mL  of acetone  through the
           cartridge, in the direction  opposite  to sample flow, using a
           glass syringe.  A flow rate of  approximately 0.5 mL/minute
           is employed  and the  eluate is  collected in  a 2-mL  volumetric
           flask.
     10.4  Desorption is halted once  the volumetric flask is  filled to
           the mark.   The sample is  then  transferred to a 1-dram vial
           having a Teflon®-lined screw cap  and  refrigerated  until
           analysis.   The vial  is wrapped with aluminum foil  to prevent
           photolytic decomposition of the NDMA.

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                                  T07-8
11.  GC/MS Analysis

     Although  a variety  of  GC  detectors  can  be  used for NDMA determination,
     the  following  procedure assumes the use of GC/MS in the selected ion
     monitoring (SIM)  mode.

     11.1   Instrument  Setup

           11.1.1   Considerable variation in instrument configuration
                   is  expected from one  laboratory to another.  There-
                   fore, each laboratory must be responsible for veri-
                   fying that its particular system yields  satisfactory
                   results.   The GC/MS system must be capable of accom-
                  modating  a fused-silica capillary column, which can be
                   inserted  directly into the ion  source.   The system must
                  be capable of acquiring and  processing data  in  the
                  selected  ion monitoring mode.
          11.1.2  Although  alternative column  systems can  be  used,  a
                  0.2  mm I.D.  x 50 m  Carbowax  20M fused-silica  column
                  (Hewlett-Packard Part  No.  19091-60150, or equivalent)
                  is recommended.   After installation, a helium carrier
                  gas  flow  of  2 ml per minute  is  established and  the
                 column  is  conditioned  at 250°C  for 16 hours.  The
                 injector  and  GC/MS transfer  line temperatures should
                 also be set at 250°C.
          11.1.3  The  MS and data  system are set  up according to manu-
                 facturer's specifications.  Electron impact ionization
                 (70  eV) should be employed.  Once the entire GC/MS
                 system is set up, it is calibrated as described in
                 Section 11.2.  The user should prepare a detailed
                 standard operating procedure (SOP) describing this
                 process for the particular instrument being used.

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                             T07-9
11.2  Instrument Calibration
      11.2.1  Tuning and mass standardization  of  the MS  system  is
              performed according to manufacturer's instructions
              and relevant information from the user-prepared  SOP.
              Perfluorotributyl amine should generally  be employed
              for this purpose.  The material  is introduced
              directly into the ion source through a  molecular
              leak.  The  instrumental parameters (e.g., lens,
              voltages, resolution, etc.) should be adjusted to
              give  the  relative  ion abundances shown in Table 1 as
              well  as  acceptable resolution and  peak shape.  If
              these approximate  relative  abundances cannot be
              achieved, the  ion  source may  require cleaning
              according to manufacturer's instructions.   In the
              event that the user's instrument cannot achieve  these
               relative ion  abundances, but  is otherwise operating
               properly, the  user may adopt  another set  of relative
               abundances as  performance  criteria. However, these
               values must be repeatable  on a  day-to-day basis.
      11.2.2   After the mass standardization  and tuning process has
               been completed and the appropriate values entered
                into the data system, the  user should set the SIM
                monitoring parameters (i.e., mass centroid and window
                to be monitored)  by  injecting  a moderatley high level
                standard solution (100 ug/mL)  of  NDMA onto the  6C/MS in
                the  full  scan mode.  The  scan  range should be 40 to 200
                amu  at  a rate of  0.5 to 0.8  scans/second.  The  nominal
                mass 42, 43,  and  74  amu ions are  to be used for SIM
                monitoring, with  the 74 amu  ion employed for NDMA quan-
                tification.

-------
                              T07-10
        11.2.3  Before injection of NDMA standards, the GC oven
               temperature is stabilized at 45°C.  The filament and
               electron multiplier voltage are turned off.  A 2-uL
               aliquot of an appropriate NDMA standard, dissolved in
               acetone,  is injected onto the GC/MS system using the
               splitless injection technique.  Concentrated NDMA
               standards can be purchased  from chemical  supply
               houses.  The standards  are  diluted to  the  appropriate
               concentration with  acetone.   CAUTION:   NDMA is a
               suspected carcinogen and  must  be  handled according to
               OSHA regulations.   After  five  minutes,  the  electron
               multiplier  and filament are  turned  on,  data  acquisition
               is  initiated,  and the oven temperature  is programmed
               to  250°C  at  a  rate  of 16°C/minute.  After elution  of
               the NDMA  peak  from  the GC/MS (Figure 3), the data
               acquisition  process  can be halted and data processing
               initiated.
       11.2.4   Once the  appropriate SIM parameters have been estab-
               lished, as described in Section 11.2.2, the instrument
               is  calibrated by analyzing a range of NDMA standards
               using the SIM prodecure.  If necessary, the electron
              multiplier voltage or amplifier gain can be adjusted
              to  give the desired sensitivity for standards
              bracketing the range of  interest.   A calibration
              curve of m/e 74 ion intensity versus quantity of NDMA
              injected is constructed  and  used to calculate NDMA
              concentration in the samples.

11.3  Sample Analysis

      11.3.1  The  sample analysis  process  is  the same  as that de-
              scribed in Section 11.2.3  for calibration standards.
              Samples should  be  handled  so  as  to minimize  exposure
              to light.

-------
                                 T07-11
          11.3.2  If a peak is observed for NDMA (within ±6 seconds of
                  the expected retention time), the areas (integrated
                  ion intensities) for m/e 42, 43, and 74 are
                  calculated.  The area of the m/e 74 peak is used to
                  calculate NDMA concentration.  The ratios of
                  m/e 42/74 and 43/74 ion intensities are used to
                  determine the certainty of the NDMA identification.
                  Ideally, these  ratios should be within ±20% of the
                  ratios  for  an NDMA standard in order to have
                  confidence  in the peak  identification.  Figure 4
                  illustrates the MS scan  for N-nitrosodimethylamine.

12.  Calculations

     12.1  Calibration Response Factors

           12.1.1  Data from calibration standards  are used  to calculate
                   a response factor for NDMA.  Ideally, the process
                   involves analysis of at least three calibration
                   levels of NDMA during a given day and determination
                   of the response factor (area/ng injected) from the
                   linear least squares fit of a plot of nanograms in-
                   jected versus area (for the m/e 74 ion).  In general,
                   quantities of NDMA greater than 1000 nanograms should
                   not be injected because of column overloading and/or
                   MS response nonlinearity.
            12.1.2   If substantial nonlinearity is present in the cali-
                   bration curve, a nonlinear least squares fit (e.g.,
                   quadratic)  should be employed.  This  process involves
                    fitting the data to the following  equation:

                         Y =  A + BX + CX2

-------
                             T07-12
      where
             Y = peak area
             X « quantity of NDMA (ng)
             A. B, and C are coefficients  in the equation

12.2  NDMA Concentration

      12.2.1  Analyte quantities  on  a  sample  cartridge are
             calculated  from the following equation:
     where
                    = A + BXA + CXA2
            YA  is the area of the m/e 74 ion for the sample
                injection.
            XA  is the calculated quantity of NDMA (ng)  on the
                sample cartridge.
            A, B,  and C are the coefficients calculated  from the
            calibration curve described in Section 12.1.2.
     12.2.2 If instrumental  response is essentially linear over
            the concentration range  of interest,  a linear  equation
            (C=0 in the equation  above)  can  be employed.
     12.2.3 Concentration  of analyte in  the  original  air sample
            is calculated  from  the following  equation:
                 C
     where
           CA   is the calculated concentration of analyte (ng/L).
           Vs and XA are as previously defined in Sections 9.11
           and  12.2.1, respectively.

-------
                                 T07-13
13.  Performance Criteria  and  Quality  Assurance
     This section summarizes required  quality  assurance  (QA) measures and
     provides guidance concerning performance  criteria that  should  be
     achieved within each  laboratory.

     13.1  Standard Operating Procedures  (SOPs).

           13.1.1  User should generate SOPs describing  the
                   following activites in their laboratory:
                   1) assembly, calibration, and operation
                   of the sampling system with make and model  of
                   equipment used; 2) preparation, purification,
                   storage, and handling of Thermosorb/N cartridges
                   and samples; 3) assembly, calibration, and operation
                   of  the GC/MS  system with make and model of equipment
                   used;  and 4)  all aspects of data recording and
                    processing, including  lists of  computer  hardware
                    and software  used.
            13.1.2  SOPs  should provide specific  stepwise  instructions
                    and should be readily  available to and  understood
                    by the laboratory  personnel  conducting  the work.

      13.2  Sample Collection

            13.2.1  During each sampling  event, at least one clean
                    cartridge will accompany the samples to the field and
                    back to the laboratory, having been placed in the
                    sampler but without sampling air, to serve as a field
                    blank.  The average amount of material found on the
                    field blank cartridges may be  subtracted from the
                    amount  found on the actual samples.  However, if the
                    blank level  is greater than 25% of the sample amount,
                    data  for  that component must be identified as  suspect
             13.2.2 During  each  sampling  event, at least one set of
                    parallel  samples  (two or  more  samples  collected
                     simultaneously) should  be collected.   If agreement

-------
                              T07-14
               between  parallel  samples  is not generally within
               +25%, the  user  should collect parallel samples on a
               much more  frequent basis  (perhaps for all sampling
               points;.
       13.2.3   Backup cartridges (two cartridges in series) should
               be collected with each sampling event.  Backup car-
               tridges  should  contain less than 10% of the amount
               of NDMA  found- in the front cartridges, or be equiva-
               lent to the blank cartridge level, whichever is
               greater.
       13.2.4   NDMA recovery for spiked cartridges  (using a solution-
               spiking technique) should be determined  before initial
               use of the method on real  samples.  Currently available
               information indicates that a recovery of 75% or greater
              should be achieved.

13.3  GC/MS Analysis

      13.3.1  Performance criteria  for  MS  tuning and mass  standard-
              ization  are discussed in  Section 11.2 and  Table 1.
              Additional  criteria  can be used by the laboratory, if
              desired.   The  following sections provide performance
              guidance  and suggested criteria for  determining the
              acceptability of the  GC/MS system.
      13.3.2  Chromatographic  efficiency should  be evaluated  daily
              by  the injection of NDMA calibration standards.  The
              NDMA peak should be plotted on an  expanded time scale
              so  that its width  at  10% of the peak height can be
              calculated, as shown  in Figure 5.  The width of the
              peak at 10% height should not exceed 10 seconds.  More
              stringent criteria may be required for certain appli-
              cations.  The asymmetry factor (see Figure 5) should
              be between 0.8 and 2.0.

-------
                       T07-15
13.3.3  The detection limit  for NDMA  is  calculated  from the
        data obtained for calibration standards.  The
        detection limit is defined  as
             DL = A + 3.3S

where
        DL  is the calculated detection limit in nanograms
            injected.
        A  is the intercept calculated in Section 12.1.2.
        S  is the standard deviation  of replicate determina-
           tions of the lowest-level  standard (at least three
           such determinations  are required).  The  lowest-level
           standard should yield a signal-to-noise  ratio  (from
           the total  ion  current response) of approximately 5.
 13.3.4   Replicate  GC/MS  analysis of  NDMA standards and/or
         sample extracts  should be conducted on a daily basis.
         A precision  of +15%  RSD.or better should be achieved.

-------
                                  T07-16


                                REFERENCES
(1)  Marano, R. S.,  Updegrove,  W.  S..  and  Machem,  R.  C.,   "Determination
     of Trace Levels of Nitrosamines  in Air   by  Gas   Chromatography/Low
     Resolution Mass Spectrometry," Anal.  Chem., 54,  1947-1951  (1982).

(2)  Fine, D. H., et. al,  "N-Nitrosodimethylamine   in Air,"   Bull.   Env.
     Cont. Toxicol., 1J5,  739-746  (1976).

(3)  "EPA Method 607 - Nitrosamines,"  Federal  Register, 49,  43313-43319.
     October 26, 1984.                                 ~

(4)  Anderson, R. J., "Nitrogen-Selective  Detection in Gas Chromatography,"
     Tracer Inc. Applications  Note 79-3, Austin, Texas.

(5)  Annual  Book of  ASTM   Standards,  Part  11.03, "Atmospheric Analysis,"
     American Society for  Testing  and  Materials, Philadelphia,  Pennsylvania,

(6)  Riggin, R. M.,  "Technical  Assistance  Document  for Sampling and
     Analysis of Toxic Organic  Compounds in Ambient Air,"  EPA-600/4-83-
     027, U.S. Environmental Protection Agency, Research Triangle Park,
     North Carolina, 1983.

-------
                              T07-17
                    MASS FLOW
                    CONTROLLERS
          OILLESS
           PUMP
      VENT
                                      Coupling to
                                      connect
                                      Thermosorb® N
                                      Adsorbent Cartridges
                       (a) MASS FLOW CONTROL
                    ROTAMETER

DRY
TEST
METER



"**
1




PUMP



iv
^

1*1




1 1
IEEDLE
yALVE
VENT
  (DRY TEST METER SHOULD NOT BE USED
  FOR FLOW OF LESS THAN 500 ml/mmut«)
                     (b) NEEDLE VALVE/DRY TEST METER
coupling to
connect
Thermosorb® N
adsorbent
cartridge
     FIGURE 1. TYPICAL SAMPLING SYSTEM CONFIGURATION

-------
 PROJECT:


 SITE:
LOCATION:
INSTRUMENT MODEL NO:


PUMP SERIAL NO: 	


SAMPLING DATA
                                       T07-18


                                SAMPLING DATA SHEET
                             (One Sample per Data Sheet)
                                           DATES(S) SAMPLED:
                                          TIME PERIOD  SAMPLED:


                                          OPERATOR:
                                          CALIBRATED BY:
                      Sample Number:


                 Start Time:
                                                Stop Time:
  Total Volume Data**
Vm =  (Final - Initial) Dry Gas Meter Reading,
                                               or
                            „___ _  1
                            lOuu * (Sampling Time in Minutes)
L



L
  * Flow rate  from rotameter or soap bubble calibrator
    (specify which).

 ** Use data from dry gas meter if available.
              FIGURE 2. EXAMPLE SAMPLING DATA SHEET

-------
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m
                                 TOTAL ION CURRENT
  CJI O
  ,«
  C/) m
  > Z
     -
   go

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   S>
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   SO
   > Q
                     r\>
m
                   — o»
   o>
                        NDEA
                            NOPA
                                               RESIDUAL SOLVENT
                                    NDBA
   O m
     cn

-------
                                    C2H6N20
        Methanamme, N— methyl—N— nitroso—
                                     Me 2 NNO
100.
80-
60-
40-
20-
      10   20   30   40   50   60   70
80   9
                                                            30
            FIGURE 4. MASS SPECTROSCOPY SCAN (10 TO 150 AMV)
                     OF NDMA AT A RATE OF 0.5 TO 0.8 SCANS/SECOND

-------
                      T07-21
        Asymmetry Factor
                       BC
        Exampte Calculation:
          Peak Height - DE = 100 mm
          10% Peak Height = BD = 10 mm
          Peak Width at 10% Peak Height - AC
             AB = 11 mm
             BC = 12 mm
                              23 mm
                               12
Therefore: Asymmetry Factor = —
                                   ,
                                   1.
FIGURE 5. PEAK ASYMMETRY CALCULATION

-------
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-------
                                                            Revision 1.0
                                                            September, 1986
                               METHOD T08
                  METHOD  FOR THE  DETERMINATION OF PHENOL
             AND  METHYLPHENOLS  (CRESOLS)  IN AMBIENT AIR USING
                  HIGH  PERFORMANCE  LIQUID CHROMATOGRAPHY

1.   Scope
     1.1   This document  describes  a method  for  determination  of  phenol
           and methylphenols (cresols)  in ambient  air.  With careful
           attention to reagent purity  and  other factors,  the  method
           can detect these compounds at the 1-5 ppbv level.
     1.2   The method as written has not been rigorously  evaluated.  The
           approach is a composite of several existing methods (1-3).
           The choice of HPLC detection  system will be dependent on the
           requirements  of the individual user.  However, the UV detection
           procedure is  considered to be most generally useful for
           relatively clean samples.

 2.   Applicable  Documents

     2.1   ASTM  Standards
           D1356 - Definitions of  Terms Related to Atmospheric  Sampling
           and Analysis(4).
      2.2   Other Documents
            U.S.  EPA Technical  Assistance Document (5).

  3.   Summary of Method

      3.1    Ambient air  is drawn through two midget impingers, each con-
             taining 15 mL of 0.1 N NaOH.  The phenols are trapped as
             phenolates.
      3.2    The  impinger solutions  are  placed in a vial with  a Teflon®-
             lined  screw  cap and  returned to  the laboratory  for

-------
                                   T08-2
            analysis.  The solution is cooled in an ice bath and adjusted
            to pH <4 by addition of 1 ml of 5% v/v sulfuric acid.  The sample
            is adjusted to a final volume of 25 mL with distilled water.
      3.3   The phenols are determined using reverse-phase HPLC with
            either ultraviolet (UV) absorption detection at 274 nm,
            electrochemical  detection, or fluorescence detection.  In
            general, the UV detection approach should  be used for
            relatively clean samples.

 4.   Significance

      4.1    Phenols  are emitted  into  the  atmosphere  from chemical  opera-
            tions  and  various  combustion  sources.  Many  of  these  compounds
            are  acutely toxic, and  their  determination  in ambient  air is
            required in order  to assess human  health impacts.
      4.2    Conventional methods for phenols have generally employed
            colorimetric or  gas chromatographic techniques  with relatively
            large  detection  limits.  The method described here  reduces
            the detection limit through use of HPLC.

5.    Definitions

      Definitions used  in this document and in any user-prepared Standard
      Operating Procedures (SOPs) should be consistent  with ASTM D1356
      (5).  All abbreviations and symbols are defined within this document
      at the point of use.

6.    Interferences

     6.1   Compounds having  the  same  retention times as the compounds of
           interest  will  interfere in  the method.   Such interferences can
           often be  overcome by  altering  the separation conditions (e.g.,
           using alternative HPLC  columns  or mobile  phase compositions)  or
           detectors.   Additionally, the  phenolic  compounds of  interest
           in  this method may  be oxidized  during sampling.   Validation
           experiments  may be  required to  show that  the  four  target
           compounds are not substantially degraded.

-------
                                 T08-3
     6.2    If  interferences  are  suspected in a "dirty" sample, prelimi-
           nary  cleanup  steps may be  required to identify interfering
           compounds  by  recording infrared spectrophotometry followed
           by  specific  ion-exchange column chromatography.  Likewise,
           overlapping  HPLC  peaks may be  resolved by  increasing/decreasing
           component  concentration of the mobile phase.
     6.3    All reagents  must be  checked for contamination before  use.
7.   Apparatus
     7.1    Isocratic  HPLC system consisting of  a mobile-phase  reservoir,
           a high-pressure pump, an  injection  valve,  a  Zorbax  ODS or
           C-18 reverse-phase column, or  equivalent  (25  cm  x 4.6  mm ID),
           a variable-wavelength UV  detector  operating  at  274  nm, and  a
           data system or strip-chart recorder (Figure  1).  Amperometric
           (electrochemical) or fluorescence  detectors  may  also  be employed.
     7.2   Sampling system - capable of accurately  and  precisely sampling
           100-1000 mL/minute of ambient  air  (Figure 2).
     7.3   Stopwatch.
     7.4   Friction-top metal can,  e.g.,  one-gallon (paint can)  - to hold
           samples.
     7.5   Thermometer  - to record ambient temperature.
     7.6   Barometer (optional).
     7.7   Analytical balance - 0.1 mg sensitivity.
     7.8   Midget  impingers --jet inlet type, 25-mL.
     7.9   Suction filtration apparatus - for filtering HPLC mobile phase.
     7.10  Volumetric flasks -  100 mL and 500 mL.
     7.11  Pipettes  - various sizes, 1-10 mL.
     7.12  Helium  purge line (optional) - for degassing HPLC mobile phase.
     7.13  Erlenmeyer flask, 1  L - for preparing HPLC mobile phase.
     7.14  Graduated cylinder,  1 L - for preparing HPLC mobile phase.
     7.15  Microliter  syringe,  100-250 uL - for HPLC injection.
 8.   Reagents and  Materials
     8.1    Bottles,  10  oz,  glass, with Teflon®-lined screw cap  - for
            storing sampling reagent.
     8.2    Vials,  25 mL, with  Teflon®-lined screw cap  - for holding samples.

-------
                                   T08-4
      8.3   Disposable pipettes and bulbs.
      8.4   Granular charcoal.
      8.5   Methanol - distilled in glass or pesticide grade.
      8.6   Sodium hydroxide - analytical reagent grade.
      8.7   Sulfuric acid - analytical  reagent  grade.
      8.8   Reagent water - purified  by ion  exchange and  carbon
            filtration,  or distillation.
      8.9   Polyester filters,  0.22 urn  -  Nuclepore, or equivalent.
      8.10  Phenol, 2-methyl-,  3-methyl-, and 4-methylphenol - neat
            standards (99+ % purity)  for  instrument calibration.
      8.11  Sampling  reagent,  0.1 N NaOH.  Dissolve 4.0 grams of NaOH in
            reagent water  and  dilute  to a  final volume of 1 L.  Store
            In  a glass bottle with  Teflon®-lined  cap.
      8.12  Sulfuric  acid,  5%  v/v.  Slowly add 5 mL of concentrated
            sulfuric  acid  to 95 mL  of reagent water.
      8.13  Acetate buffer,  0.1M, pH 4.8  - Dissolve 5.8 ml of glacial
            acetic  acid and  13.6 grams of sodium acetate trihydrate in 1 L
            of  reagent water.
     8.14  Acetom'trile - spectroscopic grade.
     8.15  Glacial acetic acid - analytical  reagent grade.
     8.16  Sodium acetate trihydrate  -  analytical reagent grade.

9.   Sampling

     9.1   The  sampling  apparatus  is  assembled  and  should be  similar to
           that shown in Figure 2.  EPA Federal Reference Method 6 uses
           essentially the same sampling  system (6).   All glassware
           (e.g.,  impingers, sampling bottles, etc.) must be thoroughly
           rinsed  with methanol  and oven-dried before  use.
     9.2   Before  sample  collection,  the  entire assembly  (including
       ,   empty sample  impingers)  is installed and the flow rate checked
           at a value near the  desired  rate.  In  general, flow rates of
           100-1000 mL/minute  are useful.  Flow rates  greater than
            1000 mL/minute should not be  used because  impinger collection

-------
                            T08-5
      efficiency may decrease.  Generally, calibration is accomp-
      lished  using  a soap bubble flow meter or calibrated wet test
      meter connected  to the flow exit, assuming the entire system
      is sealed.  ASTM Method  D3686 describes an appropriate
      calibration  scheme that  does not  require a sealed-flow system
      downstream  of the pump (4).
9.3   Ideally, a  dry gas meter is  included  in the  system to record
      total flow,  if the  flow  rate is  sufficient for its use.   If a
      dry gas meter is not  available,  the operator must measure and
      record  the  sampling  flow rate  at the beginning and end of the
      sampling period  to  determine sample volume.   If  the  sampling
      time exceeds two hours,  the  flow rate should be  measured  at
      intermediate points during the sampling  period.   Ideally, a
      rotameter should be included to allow observation  of the  flow
      rate without interruption of the sampling  process.
 9.4   To collect an air sample, two clean midget impingers are
      loaded  with  15  mL of 0.1 N NaOH each and sample flow is  start-
      ed.  The following parameters are recorded on the data sheet
      (see Figure  3 for an example):  date, sampling location,  time,
      ambient temperature, barometric pressure (if available),
      relative humidity (if available), dry gas meter reading  (if
      appropriate), flow rate,  rotameter  setting,  0.1 N NaOH reagent
      batch  number, and dry gas meter and pump identification
       numbers.
 9.5   The sampler  is  allowed  to operate  for the desired period, with
       periodic  recording  of the variables listed  above.   The total
       volume should not  exceed  80 L.   The operator must ensure that
       at least  5  ml of reagent  remains  in the impinger at the  end of
       the sampling interval.   (Note;   for high  ambient temperatures,
       lower  sampling  volumes  may  be  required.)
 9.6   At the end of the  sampling  period, the  parameters  listed in Sec-
       tion 9.4 are recorded and the sample flow is stopped.   If a dry
       gas meter is not used,  the flow rate must be checked at  the end
       of  the sampling interval.  If the flow rates at the beginning and

-------
                              T08-6
       end of the sampling period differ by more than  15%,  the  sample
       should be discarded.
 9.7   Immediately after sampling,  the  impinger  is  removed  from the
       sampling system.   The  contents of the impinger  are emptied
       into a clean 25-mL glass  vial with a Teflon®-lined screw-
       cap.  The impinger is  then rinsed with 5  ml  of  reagent water
       and the rinse solution is  added  to the vial.  The vial is then
       capped, sealed with Teflon®  tape,  and placed in a friction-top
       can containing 1-2 inches  of granular charcoal.  The samples
       are stored  in  the  can  and  refrigerated until analysis.   No
       degradation  has been observed if  the  time between refrigration
       and  analysis  is less than  48 hours.
 9.8    If  a dry  gas meter or  equivalent  total flow indicator is not
       used, the average  sample flow rate must be calculated
       according to the following equation:
      where

             QA = average flow rate (ml/mlnute).
  Ql, 0.2,	QN = flow rates determined at  beginning,  end, and
                  intermediate points during sampling.
              N = number of points averaged.

9.9   The total  flow is then calculated using the  following
      equation:
                       (T2-T )  *  o

-------
                                 T08-7
          where
                 Vm = total volume (L) sampled at measured
                      temperature and pressure.
                 ?2 = stop time.
                 TI = start time.
              T2"Tl = total sampling time (minutes).
                 QA = average flow rate (ml/minute).

    9.10  The volume of air sampled is often  reported unconnected for
          atmospheric conditions  (i.e., under ambient conditions).
          However, the value should be adjusted to  standard conditions
          (25°C and 760 mm pressure)  using the following  equation:

                              x  PA
                      u   _ u  X   H
                      vs    m
                                 760    273 +  TA
           where
                  Vs  =  total  sample volume  (L) at  25°C  and  760  mm Hg
                       pressure.
                  Vm  =  total  sample volume  (L) under ambient  conditions.
                       Calculated as  in Section  9.9  or  from dry gas
                       meter  reading.
                  P/\  =  ambient pressure (mm Hg).
                  TA  =  ambient temperature  (°C).
10.  Sample Analysis

     10.1  Sample Preparation
           10.1.1 The samples are returned to the laboratory in 25-mL
                  screw-capped vials.  The contents of each vial are
                  transferred to a 25-mL volumetric flask.  A 1-mL
                  volume of 5% sulfuric acid is added and the final
                  volume is adjusted to 25 ml with reagent water.

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                             T08-8
      10.1.2 The solution is thoroughly mixed and then placed in a
             25-ml screw-capped vial  for storage (refrigerated)
             until HPLC analysis.

10.2  HPLC Analysis

      10.2.1 The HPLC  system is assembled  and  calibrated  as described
             in  Section 11.  The operating  parameters are  as follows:
                          Column:  C-18 RP
                    Mobile  Phase:  30%  acetonitrile/70%  acetate
                                   buffer solution
                        Detector:  ultraviolet, operating at
                                   274 nm
                       Flow Rate:  0.3 mL/minute
                   Retention Time:  phenol  - 9.4 minutes
                                   o-cresol  - 12.5 minutes
                                   m-cresol  - 11.5 minutes    Individual
                                   p-cresol  - 11.9 minutes

                                   phenol  -  9.4 minutes
                                   o-cresol  - 12.8 minutes     Combined
                                   m/p-cresol  - 11.9 minutes
            Before each analysis,  the detector baseline is checked
            to ensure  stable operation.
     10.2.2 A 100-uL aliquot of the sample is  drawn into  a clean
            HPLC injection syringe.  The sample  injection loop
            (50  uL) is loaded  and  an  injection is  made.   The  data
            system, if available,  is  activated simultaneously with
            the  injection and  the  point  of injection is marked on
            the  strip-chart  recorder.
   -  10.2.3  After  approximately one minute, the  injection  valve
            is returned to the  "load" position and the  syringe and
            valve  are  flushed with  water in preparation for
            the  next sample  analysis.
     10.2.4  After  elution of the last component  of interest, data
            acquisition is terminated and the  component concen-
            trations are calculated as described in Section 12.

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                                 T08-9

          10.2.5 Phenols have been successfully separated  from  cresols
                 utilizing HPLC with the above operating parameters.
                 However, meta- and para-cresols have not  been  successfully
                 separated.  Figure 4 illustrates a typical  chromatogram.
          10.2.6 After a stable baseline is achieved, the system can
                 be used for further sample analyses as described
                 above.
          10.2.7 If the concentration of analyte exceeds the linear
                 range of the instrument, the sample should be  diluted
                 with mobile phase, or a smaller volume can be  injected
                 into the HPLC.
          10.2.8 If the  retention time is not duplicated, as determined
                 by the calibration curve, you may increase or  decrease
                 the acetonitrile/water  ratio to obtain the correct elution
                 time, as specified in Figure 4.   If the elution time is
                 long, increase  the ratio; if  it is too short,  decrease
                 the ratio.
11.0  HPLC Assembly and Calibration
     11.1 The HPLC system  is assembled  and operated  according to
          Section  10.2.1.
     11.2 The HPLC mobile  phase  is  prepared  by  mixing  300 mL of  acetonitrile
          and 750  mL of  acetate  buffer,  pH 4.8.  This  mixture  is filtered
          through  a  0.22-um polyester membrane filter  in  an all-glass
          and Teflon®  suction filtration apparatus.  The  filtered  mobile
           phase is degassed by purging  with  helium for 10-15 minutes
           (100 mL/minute)  or by  heating to 60°C for 5-10  minutes in an
           Erlenmeyer flask covered with a watch glass.  A constant back
           pressure restrictor (50 psi)  or short length (6-12 inches)  of
           0.01-inch  I.D. Teflon® tubing should be  placed  after the
           detector to  eliminate further mobile phase outgassing.

-------
                              T08-10
 11.3  The mobile phase is placed in the HPLC solvent reservoir and
       the pump is set at a flow rate of 0.3 mL/minute and allowed
       to pump for 20-30 minutes before the first analysis.  The
       detector is switched on at least 30 minutes before the first
       analysis and the detector output is displayed  on  a strip-chart
       recorder or similar output device.   UV detection  at 274 nm is
       generally preferred.  Alternatively,  fluorescence  detection
       with 274-nm excitation at 298-nm emission  (2),  or  electrochemi-
       cal  detection  at 0.9 volts (glassy  carbon  electrode versus
       Ag/AgCl)  (3) may be used.   Once  a stable baseline  is achieved,
       the  system  is  ready for calibration.
 11.4   Calibration standards  are  prepared  in  HPLC  mobile  phase  from the
       neat materials.   Individual stock solutions of  100 mg/L  are
       prepared  by dissolving  10  mg  of  solid  derivative in 100 mL  of
       mobile  phase.  These  individual  solutions are used  to prepare
       calibration  standards containing  all of the phenols  and cresols
       of interest  at concentrations spanning the  range of  interest.
 11.5   Each calibration standard  (at least five levels) is  analyzed three
       times and area response is tabulated against mass injected.
       Figures 5a through  5e illustrate HPLC response to various phenol
       concentrations (1 mL/minute flow rate).  All calibration runs
       are performed as described for sample analyses  in Section 10.
       Using the UV detector, a linear response range  of approximately
       0.05 to 10 mg/L should be achieved for 50-uL injection volumes.
       The results may be used to prepare a calibration curve, as
       illustrated in Figure 6 for phenols.  Linear response is
       indicated where a correlation  coefficient  of at  least 0.999
      for a linear least-squares fit of the data  (concentration
       versus  area  response) is obtained.  The retention  times for
      each  analyte should agree  within  2%.
11.6  Once  linear  response has been  documented, an intermediate con-
      centration standard near the anticipated  levels  for each compo-
      nent,  but  at least  10 times the detection limit,  should  be chosen
      for daily  calibration.   The response for the various components
      should  be  within  10% day to day.   If greater variability is
      observed,  recalibration may be required or  a new calibration
      curve must be developed  from fresh standards.

-------
                                T08-11
   11 7  The response for each exponent In the daily calibration  standard
         is used to calculate a response factor according to the following
         equation:
                           C  x
                     RFC =
                             RC
          where
                 RFC - response  factor (usually  area  counts) for the
                       component of  interest  in  nanograms  injected/response
                       unit.
                 Cc  - concentration (mg/L)  of analyte in  the  daily call-
                       bration standard.
                 V,  = volume (uL) of calibration standard injected.
                 R^   . response  (area counts) for analyte in the calibration
                       standard.

12.  Calculations
     12.1  The concentration of  each  compound is calculated  for each
           sample using the following equation:

                       WH - RFC X Rd X !£  X ^
                        d     c    d   Vj    VA
           where
                  Wd  = total quantity of analyte (ug) in the sample.
                  RFC =  response  factor  calculated in Section 11.6.
                  Rd   =  response (area  counts or other response units)
                         for analyte  in  sample extract.
                   VE  =  final  volume (ml)  of sample  extract.
                   Vl  = volume  of extract  (uL)  injected onto  the  HPLC
                         system.
                   VD  = redilution volume (if sample was  rediluted).
                   VA  = aliquot  used for redilution (if sample was
                         rediluted).

-------
                                  T08-12
     12.2  The concentration of analyte in the original sample is
           calculated from the following equation:

                       CA =      d     x 1000
                            vm (or Vs)
           where

                  CA = concentration of analyte (ng/L)  in the original  sample.
                  Wjj = total quantity of analyte (ug)  in sample.
                  Vm = total sample volume (L) under ambient conditions.
                  Vs = total sample volume (L) at 25 °C and 760 mm Hg.
     12.3  The analyte concentrations can be converted  to ppbv using  the
           following equation:
                       CA (ppbv)  * CA (ng/L) x 24.4
                                               MWA
           where
                  CA (ng/L)  is  calculated  using Vs.
                  MWA = molecular weight of analyte.
13.  Performance Criteria and Quality Assurance
     This section summarizes required quality assurance (QA)  measures and
     provides guidance concerning performance criteria  that should  be
     achieved within each laboratory.
     1.3.1  Standard  Operating Procedures (SOPs).
           13.1.1 Users should  generate SOPs describing the following
                  activities in their laboratory:   (1)  assembly,
                  calibration,  and operation of the sampling  system,
                  with make  and model  of equipment  used;  (2)  prepara-
                  tion,  purification, storage, and  handling of sampl-
                  ing reagent and samples;  (3) assembly,  calibration,

-------
                             T08-13
             and  operation  of the  HPLC system, with make and model
             of  equipment used;  and  (4)  all aspects of data recording
             and  processing,  including lists of  computer hardware
             and  software used.
      13.1.2  SOPs should provide specific  stepwise  instructions
             and  should be  readily available to  and understood
             by  the laboratory personnel  conducting the work.
13.2  HPLC System Performance
      13.2.1  The general  appearance  of the HPLC  chromatogram should
             be  similar to  that  illustrated in  Figure 4.
      13.2.2  The HPLC system  efficiency  and peak asymmetry  factor
             should be determined in the following  manner:  A
             solution of  phenol  corresponding to at least  20 times
             the detection  limit should  be injected with the  re-
             corder chart  sensitivity and speed  set to yield  a peak
             approximately  75% of full  scale  and 1  cm wide  at  half
             height.  The peak asymmetry factor is  determined  as
             shown in Figure  7, and  should be betweeen 0.8  and 1.8.
      13.2.3  HPLC system  efficiency  is  calculated according to the
             following equation:

                  N = 5.54

            where
                     N    =  column efficiency   (theoretical plates).
                     tr   =  retention time (seconds)  of analyte.
                     wl/2 = widtn of component   peak at half height
                             (seconds).
             A column efficiency of >5,000 theoretical plates
             should be obtained.
      13.2.4 Precision of  response  for replicate HPLC injections
             should be +10%  or  less, day to day, for calibration
             standards.  Precision  of retention times should be
             +2%, on a given day.

-------
                             T08-14
 13.3   Process  Blanks
       13.3.1   Before use, a 15-mL aliquot of each batch of 0.1 N
               NaOH reagent should be analyzed as described in
               Section 10.  In general, analyte levels equivalent to
               <5 ng/L in an 80-L sample should be achieved.
       13.3.2   At least one field blank, or 10% of the field samples,
               whichever is larger, should be shipped and analyzed
               with each group of samples.  The number of samples
              within a group and/or time frame should be recorded
               so that a specified percentage of blanks is  obtained
              for a given number of field samples.   The field blank
              is treated identically to the  samples  except that no
              air is drawn through the reagent.   The same  performance
              criteria  described in Section  13.3.1 should  be  met  for
              process blanks.
13.4  Method Precision  and Accuracy
      13.4.1  At least  one duplicate sample,  or  10%  of the field
              samples,  whichever is  larger,  should be  collected
              during  each  sampling  episode.   Precision for field
              replication  should be ±20%  or  better.
      13.4.2  Precision  for  replicate  HPLC injections  should  be
             _+10%  or better, day  to day, for calibration
              standards.
      13.4.3  At  least one spiked  sample, or  10% of  the  field
              samples, whichever is  larger, should be  collected.
              The impinger solution  is  spiked with a known quantity
              of the compound of interest, prepared  as a dilute
             water solution.  A recovery of >80% should be achieved
              routinely.
      13.4.4  Before initial use of the method, each laboratory
             should generate triplicate spiked samples at a
             minimum of three concentration levels,  bracketing the
             range of interest  for each compound.  Triplicate
             nonspiked samples must also be processed.  Spike
             recoveries of >80 ±10% and blank levels of <5 ng/L
             (using an 80-L sampling volume) should  be achieved.

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                                 T08-15


                                REFERENCES


(1)   NIOSH P &  CAM  Method  S330-1, "Phenol,"  National  Institute of
     Occupational Safety and  Health,  Methods Manual,  Vol.  3,  1978.

(2)   Ogan, K. and,  Katz, E..  "Liquid  Chromatographic  Separation  of
     Alkylphenols with Fluorescence and  Ultraviolet Detection,"  Anal.
     Chem., E.3, 160-163 (1981).

(3)   Shoup, R.  E.f  and Mayer, G. S.,  "Determination of  Environmental
     Phenols by Liquid Chromatography Electrochemistry," Anal. Chem.,
     54, 1164-1169  (1982).

(4)   Annual Book of ASTM  Standards, Part 11.03,  "Atmospheric  Analysis,"
     American Society for  Testing and Materials,  Philadelphia,
     Pennsylvania,  1983.

(5)   Riggin, R. M., "Technical  Assistance Document for  Sampling  and
     Analysis of Toxic Organic Compounds in Ambient Air,"  EPA-600/4-83-
     027, U.S.  Environmental  Protection  Agency,  Research Triangle  Park,
     North Carolina, 1983.

(6)   "Method 6  Determination  of S02  Emissions  from Stationary Sources,"
     Federal Register, Vol. 42.. No.  160. August, 1977.

-------
                       INJECTION
                        VALVE
 MOBILE
 PHASE
RESERVOIR
                                       COLUMN
                                            VARIABLE
                                          WAVELENGTH
                                              UV
                                            DETECTOR
  TO
WASTE
                                DATA
                               SYSTEM
STRIPCHART
 RECORDER
                                                                                  o
                                                                                  oo
                                                                                  Cfi
                     FIGURE 1. TYPICAL HPLC SYSTEM

-------
                                           SILICA GEL
                                SAMPLE

                               IMPINGERS
                  ROTAMETER
VENT
          DRY

          TEST

          METER
PUMP
                                                              0.1 N NaOH
                                            o
                                            00
                                            I
           FIGURE 2. TYPICAL SAMPLING SYSTEM FOR MONITORING

                     PHENOLS/CRESOLS IN AMBIENT AIR

-------
                                       T08-18
PROJECT:

SITE:
LOCATION:
INSTRUMENT MODEL NO:

PUMP SERIAL NO: 	

SAMPLING DATA
                                SAMPLING DATA SHEET
                            (One Sample per Data Sheet)
DATES(S) SAMPLED:
TIME PERIOD SAMPLED:

OPERATOR:
CALIBRATED BY:
                      Sample Number:
                 Start Time:
  Stop Time:
Time
1.
2.
3.
4.
N.
Dry Gas
Meter
Reading





Rotameter
Reading





Flow
Rate,*0
mL/min





Ambient
Temperature
°C





Barometric
Pressure,
mm Hg





Relative
Humidity, %





Comments





  Total Volume  Data**
     Vm = (Final - Initial)  Dry Gas Meter Reading, or
              Q2 + Q3 "•  0N
                                               _
                             1000 * (Sampling Time in Minutes)
   * Flow rate  from rotameter or soap bubble calibrator
     (specify which).
  ** Use data from dry gas meter if available.
              FIGURE 3. EXAMPLE SAMPLING  DATA  SHEET

-------
                           T08-19
                        O
                        ro
      OPERATING PARAMETERS
                HPLC
Column: C-18 RP
Mobile Phase: 30% Acetonitrile/70% Acetate Buffer
Detector: Ultra violet operating at 274 nm
Flow Rate: 1 ml/min
Retention Time: 3.4 minutes
            M/P-CRESOL-**
                               0-CRESOL
                                 JUL. 30, 1986 15:07:17 CHART 0.50 CM/MIN
                                                RUN *43  CALC fO
                                 COLUMN          SOLVENT  OPR ID:
                                 EXTERNAL STANDARD QUANTITATION
                                        AMOUNT RT   EXP RT
                                       790.82600  8.81
                                      2686.95000 11.30
                                      1645.46000 12.22
                                      5123.24000
                          AREA      RF
                         790826 L  O.OOOOOOEO
                         2686966 F  O.OOOOOOEO
                         1645466 L  O.OOOOOOEO
O
LU
         TIME
    FIGURE 4. TYPICAL CHROMATOGRAM ILLUSTRATING
                SEPARATION OF PHENOLS/CRESOLS  BY HPLC

-------
                           T08-20
                               (b)

                              3.43
                                   (O

                                   3.39
              (a)

              3.39
                           O
                           LJ
                TIME
TIME-
                  (d)

                 3.44
              (VI
              cvi
                      (e)

                     3.39
                                          CONC.
                                 AREA
                                COUNTS
                                                249054
                                                554609
                                                804918
                                               1038422
                                               1296781
            u
            UJ
TIME
4/tg
                                  TIME
FIGURE 5a-5e. HPLC CHROMATOGRAM OF VARYING
             PHENOL CONCENTRATIONS

-------
                              T08-21
     o
     o
     10
Column: C-18 RP
Mobile Phase: 30% Acetonitrile/70% Acetate Buffer
Detector: Ultra violet operating at 274 nm
Flow Rate:  1 ml/min
Retention Time:  3.4 minutes
D
O
O
     O
     O
     o
LU
DC
     o
     o
     ID
                         CORRELATION COEFFICIENT:
                                   0.999
                         T
                          2
                       3       4

                    PHENOL  (pg)
          FIGURE 6. CALIBRATION CURVE FOR PHENOL

-------
                         T08-22
         Asymmetry Factor
BC
AS
         Example Calculation:
          Peak Haight « DE » 100 mm
          10% Paak Height • SO » 10 mm
          Peak Width at 10% Peak Height - AC
             AB * 11 mm
             BC « 12 mm
               23 mm
         Therefore: Asymmetry Factor * ~
            1.1
FIGURE 7. PEAK ASYMMETRY CALCULATION

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                                                             Revision 1.1
                                                             June, 1988
                                 METHOD T09
          METHOD FOR THE DETERMINATION OF POLYCHLORINATED DIBENZO-
         p D OXINS (PCDDs) IN AMBIENT AIR USING HIGH-RESOLUTION GAS
        CHROMATOGRAPHY/HIGH-RESOLUTION MASS SPECTROMETRY (HRGC/HRMS)
1.   Scope
    1.1  This document describes a method for the determination of
         polychlorinated dibenzo-p-dioxins (PCDDs) in ambient air.   In
         particular, the following PCDDs have been evaluated in the
         laboratory utilizing this method:
           o  l,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD)
           o  l,2,3,4,7,8-hexachlorodibenzo-p-dioxin (1,2,3,4,7,8-HXCDD)
           o  Octachlorodibenzo-p-dioxin (OCDD)
           o  2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD)
         The method consists of  sampling ambient  air via an inlet filter
         followed  by  a  cartridge (filled with  polyurethane foam)  and
         analysis  of  the  sample  using  high-resolution  gas chromatography/
         high-resolution  mass  spectrometry  (HRGC/HRMS).   Original laboratory
         studies have indicated  that the use of polyurethane foam (PUF) or
         silica gel  in  the sampler will give equal  efficiencies for retain-
         ing  PCDD/PCDF  isomers;  i.e.,  the  median retention efficiencies
         for  the PCDD isomers  ranged from  67 to 124 percent with PUF and
         from 47 to 133 percent  with silica gel.  Silica gel,  however,
         produced  lower levels of background interferences than PUF.
         The  detection limits  were, therefore, approximately four times
         lower for tetrachlorinated isomers and ten times lower for
         hexachlorinated isomers when using silica gel  as the adsorbent.
         The difference in detection limit was approximately a factor  of
         two for the octachlorinated isomers.  However, due to variable
          recovery and extensive cleanup required with silica gel, the
         method has been written using PUF as the adsorbent.
     1.2  With careful attention to  reagent purity and other factors, the
          method can detect PCDDs in filtered air at levels below 1-5 pg/m3*.
 *Lowest levels for which the method has been validated.  Up to en order of magnitude better
  sensitivity should be achievable with 24-hour air samples.

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                              T09-2
 1.3   Average  recoveries  ranged  from 68 percent to 140 percent  in
      laboratory  evaluations  of  the method sampling ultrapure filtered
      air.   Percentage  recoveries and sensitivities obtainable  for
      ambient  air samples have not been determined.
 Applicable  Documents
 2.1  ASTM Standards
     2.1.1  Method D1356 - Definitions of Terms Relating to Atmospheric
            Sampling and Analysis.
     2.1.2  Method E260 - Recommended  Practice for General  Gas  Chro-
            matography Procedures.
     2.1.3  Method E355 - Practice  for Gas  Chromatography Terms and
            Relationships.
2.2  EPA Documents
     2'2'1   Quality Assurance Handbook  for  Air Pollution  Measurement
            Systems.  Volume  II - "Ambient Air  Specific Methods,"
            Section 2.2 - "Reference Method for the Determination  of
            Suspended  Particulates in the Atmosphere," Revision 1,
            July,  1979. EPA-600/4-77-027A.
     2'2'2-  Protocol for  the  Analysis of 2.3,7 .S-Tetrachlorodlbenzo-
            P-Dioxin by High  Resolution Gas Chromatography-High
            Resolution  Mass Spectrometry. U.S. Environmental Protection
            Agency, January,  1986, EPA-600/4-86-004.
     2'2*3   Evaluation of an  EPA High Volume Air Sampler for Polychlori-
            nated Dibenzo-p-dioxins and Polychlorinated Dibenzo-
            furans, undated report by Battelle under Contract 68-02-
           4127, Project Officers.Robert G. Lewis and Nancy K.
           Wilson, U.S. Environmental  Protection  Agency. EMSL.  Research
           Triangle Park, North  Carolina.
    2'2'4  Compendium of Methods for the Determination of Toxic Organic
           Compounds in Ambient  Air.  U.S.  Environmental  Protection
           Agency, April, 1984,  600/4-84-041.
    2'2'5  Technical  Assistance  Document  for  Sampling and Analysis of
           Toxic Organic  Compounds  in  Ambient  Air.  U.S.  Environmental
           Protection  Agency, June,  1983, EPA-600/4-83-027.

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                                 T09-3
     2.3   Other Documents
          2.3.1   General Metal Works Operating Procedures for Model PS-1
                 Sampler.  General Metal Works, Inc., Village of Cleves,
                 Ohio.
          2.3.2   Chicago Air  Quality:   PCB Air Monitoring Plan, Phase 2,
                 Illinois  Environmental Protection Agency, Division of Air
                 Pollution Control,  April, 1986,  IEPA/APC/86-011.
3.  Summary of Method
     3.1   Filters and adsorbent  cartridges  (containing  PUF)  are cleaned  in
          solvents and vacuum-dried.  The filters and  adsorbent cartridges
          are stored in screw-capped jars wrapped in  aluminum  foil  (or
          otherwise protected from light) before  careful  installation
          on a modified high volume sampler.
     3.2  Approximately 325 m3 of ambient air is  drawn through a  cartridge
          on a calibrated General Metal Works Model  PS-1  Sampler, or  equi-
          valent (breakthrough has not been  shown to  be a problem with
          sampling volumes of 325 m3).
     3.3  The amount of air sampled through the adsorbent cartridge is
          recorded, and the cartridge is placed in an appropriately
          labeled container and shipped along with blank adsorbent
          cartridges to the analytical laboratory for analysis.
     3.4  The filters  and  PUF adsorbent cartridge are extracted together
          with benzene.   The extract  is concentrated, diluted with hexane,
          and cleaned  up  using column chromatography.
     3.5  The High-Resolution Gas Chromatography/High-Resolution Mass Spect-
           rometry  (HRGC/HRMS) system  is  verified to be operating properly
          and  is calibrated  with five concentration calibration  solutions,
           each  analyzed in triplicate.
     3.6   A preliminary analysis of  a sample of  the extract is performed to
           check  the  system performance and  to ensure that the samples are
           within the calibration  range of the  instrument.   If necessary,
           recalibrate the instrument, adjust the amount  of  the sample
           injected,  adjust the  calibration  solution  concentration, and
           adjust the data processing system to reflect observed  retention
           times, etc.

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                                  T09-4
     3.7  The samples and the blanks are analyzed by HRGC/HRMS and the
          results are used (along with the amount of air sampled)  to
          calculate the concentrations of polychlorinated dioxins  in
          ambient air.
4.  Significance
     4.1  Polychlorinated dibenzo-p-dioxins  (PCDDs)  are  extremely  toxic.
          They are carcinogenic  and  are of major  environmental  concern.
          Certain isomers,  for example, 2,3,7,8-tetrachlorodibenzo-p-
          dioxin (2,3,7,8-TCDD),  have  LD50 values in  the  parts-per-tril-
          lion range  for some  animal species.   Major  sources  of these
          compounds have been  commercial  processes involving  polychlorinated
          phenols and  polychlorinated  biphenyls (PCBs).   Recently, however,
          combustion  sources have  been  shown to emit  polychlorinated
          dibenzo-p-dioxin  (PCDD), including the  open-flame combustion of
          wood  containing chlorophenol  wood preservatives, and  emissions
          from  burning transfonners  and/or capacitors that contain PCBs
          and  chlorobenzenes.
     4.2   Several  documents have been published which describe  sampling and
          analytical approaches for  PCDDs, as outlined in Section 2.2.  The
          attractive features  of these methods have been combined in this
          procedure.  This method has not  been validated in its final
          form,  and, therefore, one must use caution when employing it for
          specific applications.
     4.3   The relatively low level of PCDDs in the environment  requires
          the use  of high volume  sampling techniques to acquire sufficient
          samples  for analysis.  However, the volatility of PCDDs prevents
          efficient collection on filter media.  Consequently, this method
          utilizes both a filter  and a  PUF backup  cartridge which provides
          for efficient collection of most PCDDs.

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                                  T09-5
5.   Definitions
     Definitions used in this document and  in  any  user-prepared  standard
     operating procedures (SOPs)  should  be  consistent  with  ASTM  Methods
     D1356 and E355 (Sections 2.1.1 and  2.1.3).  All  abbreviations  and
     symbols within this document are defined  the  first time they are
     used.
6.   Interferences
     6.1  Chemicals that elute from the gas chromatographic (GC) column
          within ^10 scans of the standards or compounds of interest and
          which produce, within the retention time windows, ions with any
          mass-to-charge (m/e) ratios close enough to those of the ion
          fragments  used to  detect or quantify the analyte compounds are
          potential  interferences.  Most frequently encountered potential
          interferences  are  other  sample components that are extracted
          along with PCDDs,  e.g.,  polychlorinated biphenyls  (PCBs), metho-
          xybiphenyls,  chlorinated  hydroxydiphenylethers,  chlorinated naph-
          thalenes,  DDE, DDT, etc.   The actual  incidence of  interference
          by these compounds also depends  upon  relative concentrations,
          mass spectrometric resolution, and  chromatographic conditions.
          Because very  low levels of PCDDs must be measured, the elimina-
          tion of interferences  is essential.  High-purity reagents  and
           solvents must be used  and all  equipment must be  scrupulously
           cleaned.  Laboratory  reagent  blanks must  be analyzed  to  demon-
           strate absence of contamination  that  would  interfere  with  the
           measurements.  Column  chromatographic procedures are  used  to
           remove some coextracted sample components;  these procedures must
           be performed carefully to minimize loss of analyte compounds
           during attempts to increase their concentration relative to
           other  sample components.
      6.2   In addition to chemical interferences,  inaccurate measurements
           could  occur if PCDDs are retained on particulate matter, the
            filter, or PUF adsorbent cartridge, or are chemically changed
           during sampling and storage in  ways that are not  accurately
           measured  by adding isotopically labeled spikes  to the samples.

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                             T09-6
 6.3   The  system cannot separately quantify gaseous PCDDs and parti-
      culate PCDDs because the material may be lost from the filter
      by volatilization after collection and may be transferred to
      the  absorbent cartridge.  Gaseous PCDDs may also be adsorbed on
      particulate matter on the filter.
Apparatus
7.1  General  Metal Works  (GMW)  Model  PS-1  Sampler.
7.2  At least two Model  PS-1 sample  cartridges and filters  per PS-1
     Sampler.
7.3  Calibrated GMW Model  40 calibrator.
7.4  High-Resolution Gas  Chromatograph/High-Resolution  Mass
     Spectrometer/Data System (HRGC/HRMS/DS)
     7.4.1 The GC must be  equipped  for temperature programming,  and
           all required  accessories must  be  available,  including
           syringes,  gases,  and  a capillary  column.  The GC injection
           port must  be designed for  capillary columns.  The  use  of
           splitless  injection techniques  is  recommended.  On-
           column  injection  techniques can be used but they may
           severely reduce column lifetime for nonchemically bonded
           columns.   In this protocol, a 2-uL injection volume is
           used consistently.  With some GC injection ports, however,
           1-uL injections may produce some improvement in precision
           and chromatographic separation.  A 1-uL injection volume
           may be used if adequate sensitivity and precision can be
           achieved.
    [NOTE: If  1 uL is used as the injection volume, the injection
           volumes for all  extracts, blanks,  calibration solutions
           and performance check  samples must be 1 uL.]
    7.4.2  Gas Chromatograph-Mass Spectrometer Interface.
           The gas chromatograph  is  usually coupled directly to the
           mass spectrometer source.   The  interface may include a
           diverter valve  for shunting the column  effluent  and
           isolating the  mass spectrometer source.  All  components
           of  the  interface should be  glass or glass-lined  stainless

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                       T09-7
      steel.  The interface components should be compatible with
      300°C temperatures.  Cold spots and/or active surfaces
      (adsorption sites) in the GC/MS interface can cause peak
      tailing and peak broadening.  It is recommended that the
      GC  column  be  fitted  directly into the MS source.  Graphic
      ferrules should be avoided  in the GC injection area
      since  they may  adsorb TCDD.  Vespel® or equivalent
      ferrules are  recommended.
7.4.3 Mass Spectrometer.   The static  resolution of  the  instru-
      ment must  be  maintained at  a minimum of 10,000  (10  percent
       valley).   The mass  spectrometer must be operated  in a
       selected  ion  monitoring (SIM) mode  with a total cycle  time
       (including voltage  reset time)  of one  second  or less
       (Section  12.3.4.1).   At a minimum,  ions that  occur  at
       the following masses must be monitored:
    2,3,7,8-TCDD         1.2.3,4,7,8-HyCDD          OCDD
      258.9300               326.8521              394.7742
      319.8965               389.8156              457.7377
      321.8936               391.8127              459.7347
      331.9368
      333.93338
 7.4.4  Data System.  A dedicated computer data system is  employed
       to control the rapid multiple  ion monitoring process  and
       to acquire the data.   Quantification data (peak  areas or
       peak  heights)  and SIM  traces (displays of intensities of
       each m/z  being monitored as a  function of time)  must  be
       acquired  during the analyses.  Quantifications may be
        reported  based upon computer-generated peak  areas  or  upon
       measured  peak  heights  (chart recording).  The  detector
        zero setting must  allow peak-to-peak  measurement of the
        noise on  the baseline.

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                                T09-8
        7.4.5  GC Column.  A fused  silica  column  (30 m  x  0.25 mm  I.D.)
               coated with DB-5, 0.25 u film thickness (J & s Scientific,
               Inc.,  Crystal  Lake,  IL) is  utilized to  separate each of
               the  several  tetra- through  octa-PCDDs, as a group, from all
               of the other groups.   This  column also resolves 2,3,7,8-TCDD
               from all 21  other TCDD isomers; therefore, 2,3,7,8-TCDD
               can  be  determined quantitatively if proper calibration
               procedures are followed as per Sections 12.3 through 12.6.
               Other columns may be used  for determination of PCDDs, but
               separation of the wrong PCDD isomers must  be  demonstrated
              and documented.  Minimum acceptance  criteria  must  be
              determined as per Section  12.1.   At  the  beginning  of each
              12-hour period (after mass  resolution has  been demonstrated)
              during  which sample  extracts or  concentration  calibration
              solutions  will be analyzed,  column operating conditions
              must  be attained  for  the required separation on the
              column  to  be used for samples.
  7.5   All  required syringes, gases,  and other pertinent supplies to
       operate the  HRGC/HRMS system.
  7.6   Airtight,  labeled screw-capped containers to hold the sample car-
       tridges  (perferably  glass with Teflon seals or other noncontaminat-
       ing  seals).
  7.7   Data sheets  for each  sample  for recording the location and sample
       time, duration of sample, starting time, and volume of air sampled.
  7.8   Balance capable of weighing accurately to _+0.001 g.
  7.9   Pipettes, micropipets, syringes, burets, etc.,  to  make calibra-
      tion and spiking solutions,  dilute  samples  if  necessary, etc..
      including syringes for accurately measuring  volumes  such
      as 25 uL and  100 uL  of isotopically  labeled  dioxin solutions.
7.10  Soxhlet extractors capable of extracting GMW PS-1  PUF  adsorbent
      cartridges  (2.3" x 5" length),  500-mL  flask, and condenser.

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                             T09-9
7.11  Vacuum drying oven system capable  of maintaining the  PUF  car-
      tridges being evacuated at 240 torr (flushed  with  nitrogen)
      overnight.
7.12  Ice chest - to store samples at 0°C after collection.
7.13  Glove box for working with extremely toxic standards  and
      reagents with explosion-proof hood for venting fumes  from
      solvents reagents, etc.
7.14  Adsorbtion columns for column chromatography - 1  cm x 10 cm
      and 1 cm x 30 cm, with stands.
7.15  Concentrator tubes and a  nitrogen evaporation apparatus with
      variable  flow rate.
7.16  Laboratory refrigerator with  chambers operating at 0°C
      and 4°C.
7.17  Kuderna-Danish  apparatus  -  500 ml  evaporating flask, 10 ml
      graduated  concentrator tubes  with  ground-glass stoppers,
      and  3-ball macro Snyder  Column  (Kontes  K-570001-0500,
      K-50300-0121, and K-569001-219, or equivalent).
 7.18  Two-ball  micro  Snyder Column, Kuderna-Danish (Kontes
       569001-0219, or equivalent).
 7.19   Stainless steel spatulas and  spoons.
 7.20   Minivials -  1 ml, borosilicate glass, with conical reservoir
       and screw caps  lined with Teflon-faced silicone
       disks, and a vial holder.
 7.21  Chromatographic columns for Carbopak cleanup -  disposable
       5-mL graduated  glass pipets, 6 to 7 mm ID.
 7.22  Desiccator.
 7.23  Polyester gloves for  handling PUF cartridges and filter.
 7.24  Die - to cut PUF plugs.
 7.25  Water bath  equipped with concentric  ring cover and  capable
       of being temperature-controlled within ^2°C.
 7.26  Erlenmeyer  flask, 50  ml.
 7.27  Glass vial, 40 ml.
 7.28  Cover glass petri dishes for shipping  filters.
 7.29  Fritted  glass  extraction thimbles.
 7.30  Pyrex  glass tube furnace system  for  activating silica
        gel  at  180°C under  purified  nitrogen gas purge for  an hour,
       with capability of  raising temperature gradually.

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                                   T09-10
      [NOTE:  Reuse of glassware should be minimized to  avoid  the risk  of
      cross-contamination.   All  glassware that  is  used,  especially glassware
      that 1S reused,  must  be  scrupulously cleaned as  soon  as  possible  after
      use.  Rinse  glassware with  the  last solvent  used in it and  then with
      high-purity  acetone and  hexane.   Wash with hot water  containing
      detergent.   Rinse  with copious  amount of tap  water and several
      portions  of  distilled water.  Drain,  dry, and heat in a muffle furnace
      at 400°C  for  2 to  4 hours.- Volumetric glassware must not be heated
      in a muffle  furnace; rather, it should be rinsed with high-purity
     acetone and hexane.  After the glassware is dry and cool, rinse it with
     hexane, and store  it inverted or capped with solvent-rinsed aluminum
     foil  in a clean environment.]

8.   Reagents and  Materials

     8.1   Ultrapure glass wool,  silanized, extracted with methylene
          chloride and hexane, and  dried.
     8.2   Ultrapure acid-washed  quartz  fiber  filters for PS-1
          Sampler  (Pallfex  2500  glass,  or equivalent).
     8.3   Benzene  (Burdick  and Jackson,  glass-distilled, or equivalent).
     8.4   Hexane (Burdick and  Jackson,  glass-distilled, or equivalent).
     8.5   Alumina,  acidic - extracted in  a  Soxhlet  apparatus with
          methylene chloride for 6 hours  (minimum of 3 cycles
          per hour) and  activated by heating in a foil-covered
         glass container for 24 hours at 190°C.
    8.6  Silica gel - high-purity grade, type 60, 70-230 mesh;
         extracted in a Soxhlet  apparatus with methylene chloride
         for 6 hours (minimum of 3 cycles per hour) and  activated
         by heating in a foil-covered glass container  for  24  hours
         at 130°C.
    8.7  Silica gel impregnated  with  40 percent  (by weight) sulfuric
         acid - prepared by adding  two  parts  (by  weight) concentrated
         sulfuric  acid to three  parts (by weight)  silica gel  (extracted
        and activated)  and  mixiing with a  glass  rod until  free  of lumps;
      - stored in a  screw-capped glass bottle.

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                             T09-11
8 8   Graphitized carbon black  (Carbopak  C  or  equivalent),
      surface of approximately  12 m2/g,  80/100 mesh  -  prepared  by
      thoroughly mixing 3.6 grams Carbopak  C and 16.4  grams  Celite
      545« in a 40-mL vial and  activating at 130'C for six  hours;
      stored in a desiccator.
 8.9   Sulfuric Acid, ultrapure, ACS grade,  specific gravity 1.84.
 8.10  Sodium Hydroxide, ultrapure, ACS grade.
 8 11  Native and  isotopically labeled PCDD/PCDF isomers for
      calibration and  spiking standards, from Cambridge Isotopes,
      Cambridge,  MA.
 8.12 n-decane (Aldrich Gold Label  grade [D90-1], or  equivalent).
 8.13 Toluene  (high purity,  glass-distilled).
 8 14  Acetone  (high purity,  glass-distilled).
 8.15  Filters, quartz fiber  -  Pall flex  2500 QAST, or  equivalent.
 8.16  Ultrapure nitrogen gas (Scott chromatographic grade,  or  equivalent).
 8.17  Methanol (chromatographic grade).
 8 18  Methylene  chloride (chromatographic  grade, glass-distilled).
  8 19  Dichloromethane/hexane (3:97, v/v), chromatographic grade.
  8.20  Hexane/dichloromethane (1:1, v/v), chromatogtraphic grade.
  8.21  Perfluorokerosene  (PFK),  chromatographic grade.
  8 22  Celite  545®, reagent  grade,  or equivalent.
  8.23  Membrane  filters or filter paper  with  pore sizes less than
        25 urn,  hexane-rinsed.
  8 24  Granular anhydrous sodium sulfate,  reagent grade.
  8*.25  Potassium carbonate-anhydrous,  granular, reagent  grade.
  8.26  Cyclohexane, glass-distilled.
  8.27  Tridecane,  glass-distilled.
  8.28  2,2,3-trimethylpentane, glass-distilled.
  8.29  Isooctane,  glass-distilled.
  8.30  Sodium sulfate, ultrapure, ACS grade.
   8.31  Polyurethane  foam -  3 inches thick sheet stock, polyether
        type used in  furniture  upholstering, density  0.022 g/cm .

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                              T09-12
 8.32  Concentration  calibration  solutions  (Table  1) - four tridecane
       solutions  containing  13Cl2-l,2,3,4-TCDD  (recovery standard)
       and  unlabeled  2,3,7,8-TCDD at varying concentrations, and
         C12-2,3.7,8-TCDD  (internal standard, CAS  RN 80494-19-5).
       These  solutions must  be obtained from the Quality Assurance
       Division,  U.S. EPA. Environmental Monitoring Systems Laboratory
       (EMSL-LV), Las Vegas, Nevada, and must be used to calibrate
       the  instrument.  However, secondary standards may be obtained
       from commercial sources, and solutions may be prepared in the
       analytical laboratory.  Traceability of standards must be
       verified against EPA-supplied standard solutions by procedures
      documented in laboratory SOPs.   Care must be taken to use the
      correct standard.  Serious overloading of instruments may occur
      if concentration calibration solutions intended  for low-resolution
      MS are injected into the high-resolution MS.
8.33  Column performance check mixture dissolved in 1  mL of tridecane
      from Quality Assurance Division  (EMSL-LV).  Each ampule  of this
      solution will  contain  approximately  10 ng of the following
      components (A)  eluting near 2,3,7,8-TCDD and of  the  first (F)
      and last-eluting (L) TCDDs,  when using the recommended columns
      at a concentration of  10 pg/uL of each of these  isomers:
           o   unlabeled  2,3,7,8-TCDD
           o   13C12-2,3,7,8-TCDD
           o   1,2,3,4-TCDD (A)
           o   1,4,7,8-TCDD (A)
           o   1,2,3,7-TCDD (A)
           o   1,2,3,8-TCDD (A)
           o   1,3,6,8-TCDD (F)
           0   1,2,8,9-TCDD (L)
      If these solutions are unavailable from EPA. they  should  be
      prepared by the analytical laboratory or a chemical supplier
      and analyzed in a manner traceable to the EPA performance
      check mixture designed for 2,3,7,8-TCDD monitoring.  Similar
     mixtures of isotopically labeled compounds should be prepared
     to check performance for monitoring  other specific forms  of
     TCDD that are of interest.

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                             T09-13
8.34  Sample fortification solution - isooctane  solution  contain-
      ing the internal  standard at a nominal  concentration  of  10 pg/uL.
8.35  Recovery standard spiking solution - tridecane solution  con-
      taining the isotopically labeled standard  (13C12-2,3f7,8-TCDD
      and other PCDDs of interest) at a concentration of  10.0  pg/uL.
8.36  Field blank fortification solutions - isooctane solutions
      containing the following:
           0  Solution A:  10.0 pg/uL of unlabeled 2,3,7,8-TCDD
           0  Solution B:  10.0 pg/uL of unlabeled 1,2,3,4-TCDD
[NOTE:  These reagents and the detailed analytical procedures described
herein  are designed for monitoring TCDD isomer concentrations of
6.0  pg/m3 to 37 pg/m3 each.   If ambient concentrations should exceed
these levels, concentrations  of calibrations and spiking solutions
will need to be modified,  along with the  detailed sample preparation
procedures.  The  reagents  and procedures  described herein  are based
on  Appendix  B of  the Protocol  for  the Analysis of 2,3,7,8-TCDD
 (Section  2.2.2) combined with the  evaluation of the  high volume air
 sampler for  PCDD.
 Preparation  of  PUF  Sampling  Cartridge
 9.1  The PUF adsorbent  is  a  polyether-type polyurethane  foam  (density
      No.  3014 or  0.0225 g/cm3) used  for furniture upholstery.
 9.2  The PUF inserts are 6.0-cm  diameter cylindrical  plugs cut  from
      3-inch sheet stock and  should fit, with  slight compression,  in  the
      glass cartridge,  supported  by the wire screen  (Figure 1).   During
      cutting, the die  is rotated at high speed  (e.g., in a drill
      press) and continuously lubricated with water.
 9.3  For initial  cleanup, the PUF plug is placed  in a Soxhlet appara-
      tus and extracted with acetone for 14-24 hours at approximately
      4 cycles per hour.  When cartridges are reused, 5%  diethyl
      ether in n-hexane can be used as the cleanup solvent.
 9,4  The extracted PUF is placed in a vacuum oven connected to a
      water aspirator and dried at room temperature for approximately
      2-4 hours (until no  solvent odor is detected).

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num
                                   T09-14
      9.5  The PUF is placed into the glass sampling cartridge using poly-
           ester gloves.  The module is wrapped with hexane-rinsed alumi
           foil, placed in a labeled container, and tightly sealed.
      9.6  At least one assembled cartridge from each batch must  be
           analyzed, as a laboratory blank, using the procedures  described
           in Section 11, before the batch is  considered  acceptable for
           field use.  A blank  level  of <10 ng/plug for  single compounds
           is considered to  be  acceptable.
10.   Sample  Collection
      10.1  Description  of Sampling  Apparatus
           10.1.1   The  entire  sampling  system  is  diagrammed in Figure 2.
                    A unit specifically  designed  for  this method  is
                   commercially  available  (Model  PS-1 - General  Metal
                   Works, Inc.,  Village of Cleves, Ohio).
           10.1.2  The  sampling  module  (Figure 1) consists of a  glass sampl-
                   ing  cartridge and an air-tight metal  cartridge holder.
                   The  PUF is retained  in the glass sampling cartridge.
      10.2  Calibration  of Sampling System
           10.2.1  The  airflow through the sampling system is monitored
                   by a Venturi/Magnehelic assembly, as  shown in  Figure 2.
                   Assembly must be audited every six months using an
                   audit calibration orifice,  as described in the U.S.
                   EPA High  Volume Sampling Method, 40 CFR 50, Appendix  B.
                   A single-point calibration  must be performed before
                   and after each sample collection,  using the procedure
                   described in Section. 10.2.2.
           10.2.2  Prior to  calibration, a "dummy" PUF cartridge  and filter
                   are placed in the sampling  head and the sampling  motor
                   is activated.   The  flow control  valve  is  fully opened
                   and the voltage  variator is  adjusted so  that a sample
                   flow  rate  corresponding to  110% of the  desired flow rate
                   is indicated  on  the Magnehelic  (based  on  the previously
                   obtained multipoint calibration  curve).  The   motor is
                   allowed to warm up for  10 minutes  and then  the flow control

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                            T09-15
            valve is adjusted to achieve the desired flow rate.  The
            ambient temperature and barometric pressure should be
            recorded on an appropriate data sheet.
    10.2.3  The calibration orifice is placed on the sampling
            head and a manometer is attached to the tap on the
            calibration orifice.  The sampler is momentarily
            turned off to set the zero level of the manometer.
            The sampler is then switched on and the manometer
            reading is recorded after a stable reading is
            achieved.  The sampler is then shut off.
    10.2.4  The calibration curve for the orifice is used to cal-
            culate sample flow  from the data obtained in Section
            10.2.3, and the calibration curve for the Venturi/
            Magnehelic assembly is used to calculate sample flow
            from the data obtained in Section 10.2.2.  The calibra-
            tion data should be recorded on an appropriate data
            sheet.   If the two  values do not  agree  within 10%, the
            sampler should be inspected for damage, flow blockage,
            etc.   If  no obvious problems are  found, the  sampler
            should be recalibrated (multipoint) according to the
            U.S. EPA  High  Volume  Sampling Method  (Section 10.2.1).
     10.2.5  A multipoint calibration  of the calibration  orifice,
            against  a primary  standard, should  be  obtained  annually.
10.3  Sample Collection
     10.3.1  After  the  sampling  system has been  assembled  and
            calibrated  as  described  in  Sections 10.1  and  10.2, it
            can be used to  collect air  samples, as  described  in
            Section  10.3.2.
     10.3.2. The samples  should  be located  in  an unobstructed  area,
            at least  two  meters from any  obstacle to  air flow.
             The exhaust  hose should  be  stretched  out  in  the down-
             wind direction  to prevent recycling of air.

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                         T09-16
 10.3.3  A clean PUF sampling cartridge and quartz filter are
         removed from sealed transport containers and placed in
         the sampling head using forceps and gloved hands.   The
         head is tightly sealed into the sampling system.  The
         aluminum foil  wrapping is placed back  in the sealed
         container for  later use.
 10.3.4  The zero reading of the Magnehelic  is  checked.   Ambient
         temperature, barometric pressure,  elapsed time meter
         setting, sampler serial number,  filter number, and
         PUF  cartridge  number are  recorded on a suitable  data
         sheet,  as  illustrated  in  Figure  3.
 10.3.5  The  voltage  variator and  flow control  valve  are  placed
         at the  settings  used in Section  10.2.3, and  the  power
         switch  is  turned on.  The elapsed time meter is  acti-
         vated and  the  start  time  is recorded.  The flow  (Magne-
         helic setting)  is adjusted, if necessary, using the
         flow control valve.
 10.3.6   The Magnehelic  reading is recorded every six hours
        during the sampling  period.  The calibration curve
         (Section 10.2.4) is  used to calculate the flow rate.
        Ambient temperature and barometric pressure are
        recorded at the beginning  and end of the sampling
        period.
10.3.7  At the end of the desired  sampling period, the power is
        turned off and  the filter  and PUF cartridges  are  wrapped
        with the original  aluminum fail  and  placed in sealed,
        labeled containers  for transport  back to the  laboratory.
10.3.8  The  Magnehelic  calibration is  checked using the cali-
        bration  orifice,  as  described  in  Section 10.2.4.  If
        calibration deviates by  more than 10% from the  initial
        reading, the  flow data  for that  sample  must be marked
        as suspect  and  the sampler should be inspected and/or
        removed  from  service.

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                                 T09-17

          10.3.9   At  least one field filter/PUF blank will be returned to
                  the laboratory with each group of samples.  A field
                  blank  is treated exactly as a sample except that no air
                  is  drawn through the  filter/PUF cartridge assembly.
          10.3.10  Samples are stored at 20°C in an ice chest until receipt
                  at  the analytical  laboratory, after which they are
                  refrigerated at 4°C.
11.  Sample Extraction
     11.1  Immediately before use, charge  the Soxhlet apparatus with 200
           to 250  ml of benzene and reflux for 2 hours.    Let the apparatus
           cool,  disassemble  it, transfer  the benzene to  a clean glass
           container,  and retain  it as  a blank for  later  analysis,  if
           required.  After  sampling, spike the cartridges and filters
           with an internal  standard  (Table 1).  After  spiking, place the
           PUF cartridge and  filter together  in the Soxhlet apparatus
           (the use  of an extraction  thimble  is optional). (The filter  and
           PUF cartridge are  analyzed together  in  order to reach detection
           limits, avoid questionable interpretation  of the data,  and mini-
           mize cost.)  Add  200 to 250 ml  of  benzene  to the apparatus  and
           relux for  18 hours at  a  rate of at  least  3  cycles  per  hour.
     11.2  Transfer the extract to a  Kuderna-Danish (K-D) apparatus,  concen-
           trate it  to 2 to 3 ml, and let  it  cool.   Rinse the  column  and
           flask with 5 ml of benzene, collecting  the rinsate  in  the concen-
           trator tube to 2 to 3 ml.   Repeat  the  rinsing and concentration
           steps twice more.  Remove  the concentrator tube from the K-D
           apparatus  and carefully reduce the extract volume to approximately
           1 ml with  a stream of nitrogen using a flow rate and distance
           above the  solution such that a gentle rippling of the solution
           surface  is observed.

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                             T09-18
11.3  Perform the following column  chromatographic  procedures  for
      sample extraction  cleanup.  These  procedures  have  been
      demonstrated to  be effective  for a mixture consisting of:
                    0   1,2,3,4-TCDD
                       1,2,3,4,7,8-HXCDD
                    0   OCDD
                    0   2,3,7,8-TCDD
      11.3.1   Prepare  an acidic silica gel column as follows (Figure 4)
              Pack a 1  cm x 10 cm chromatographic column with a glass
              wool plug, a 1-cm layer of Na2S04/K2C03 (1:1), 1.0 g of
              silica gel (Section 8.6), and 4.0 g of 40-percent (w/w)
              sulfuric acid-impregnated silica gel (Section 8.7).
              Pack a second chromatographic column (1 cm x 30 cm)
              with a glass wool plug and 6.0 g of acidic alumina
              (Section 8.5), and top it with a 1-cm layer of sodium
             sulfate (Section 8.30).  Add hexane to the columns
             until  they are free of channels and air bubbles.
     11.3.2  Quantitatively transfer the  benzene extract (1 ml)
             from the  concentrator tub to the top of the silica
             gel  column.   Rinse  the concentrator tube  with 0.5-mL
             portions  of  hexane.   Transfer the rinses  to the top of
             the  silica gel  column.
     11.3.3  Elute  the extract  from the silica gel  column  with  90  of
             ml hexane directly  into a Kudena-Danish concentrator
             tube.   Concentrate the  eluate to  0.5 ml. using  nitro-
             gen  blowdown, as necessary.
     11.3.4  Transfer  the concentrate  (0.5 ml) to the top  of the
             alumina column.  Rinse  the K-D assembly with  two
             0.5-mL  portions of hexane, and transfer the rinses to
             the  top of the alumina  column.  Elute the  alumina
             column with 18 mL hexane until the hexane  level is
             just below the top of the sodium  sulfate.  Discard the
             eluate.  Do not let the columns reach dryness
             (i.e., maintain a solvent "head").

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                        T09-19
11.3.5  Place 30 mL of 20% (v/v)  methylene  chloride  in  hexane
        on top of the alumina column  and  elute  the TCDDs  from
        the column.  Collect this fraction  in a 50-mL Erlenmeyer
        flask.
11.3.6  Certain extracts, even after  cleanup by column  chroma-
        tography, contain interferences that preclude
        determination of TCDD at low  parts-per-trillion
        levels.  Therefore, a cleanup step  is  included  using
        activated carbon which selectively  retains  planar
        molecules such as TCDDs.  The TCDDs are then removed
        from the carbon by elution with toluene.  Proceed as
        follows:  Prepare an 18% Carbopak C/Celite 545* mixture
        by thoroughly mixing 3.6 grams Carbopak C (80/100 mesh)
        and  16.4 grams Celite 545® in a 40-mL vial.  Activate
        the  mixture  at 130°C for 6 hours, and store it in a
        desiccator.   Cut  off a clean 5-mL disposable glass
        pipet  at the 4-mL mark.  Insert a plug of glass wool
        (Section 8.1) and push it to the 2-mL mark.  Add 340 mg
        of the activated  Carbopak/Celite mixture followed by
        another glass wool  plug.  Using two glass rods, push both
        glass  wool  plugs  simultaneously toward the  Carbopak/Celite
        plug to a  length  of 2.0  to 2.5 cm.  Pre-elute  the column
        with 2 ml  of toluene followed  by 1  ml  of 75:20:5 methylene
        chloride/methanol/  benzene,  1  ml of 1:1 cyclohexane in
        methylene  choride,  and  2 ml  of hexane.  The flow rate
        should be  less  than 0.5  ml per minute.  While  the column
        is still  wet with hexane,  add  the  entire elute (30  ml)
        from the alumina column  (Section 11.3.5) to the  top of
        the  column.  Rinse the  Erlenmeyer  flask that contained the
        extract twice with 1 ml of hexane  and  add  the  rinsates
        to the top of the column.  Elute the column sequentially
        with two 1-mL aliquots  of  hexane,  1 ml of  1:1  cyclohex-
         ane in methylene chloride, and 1 mL of 75:20:5 methylene

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                                   T09-20
                   chloride/mentanol/benzene.  Turn the column upside
                   down and elute the TCDD fraction into a concentrator
                   tube with 6 ml of toluene.  Warm the tube to approxi-
                   mately 60°C and reduce the toluene volume to approxi-
                   mately 1 mL using a stream of nitrogen.  Carefully
                   transfer the residue into a 1-mL minivial  and, again
                   at elevated temperature, reduce the volume to  about
                   100 uL using a stream of nitrogen.  Rinse the  concen-
                   trator tube with 3 washings using 200 uL of 1% toluene
                   in CH2C12 each time.  Add 50 uL of tridecane and store
                   the sample in a refrigerator until  GC/MS analysis is
                   performed.

12.   HRGC/HRMS System Performance Criteria

      The laboratory  must  document that the system performance  criteria
      specified in  Sections  12.1,  12.2,  and 12.3  have  been  met  before
      analysis  of samples.
      12.1   GC  Column Performance
           12.1.1    Inject 2  uL  of the  column  performance check solution
                    (Section  8.33)  and  acquire  selected  ion monitoring
                    (SIM) data for m/z  258.930, 319.897, 321.894, and
                   333.933 within  a  total  cycle time  of 
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                             T09-21
             the retention  time window  for total  TCDD determination.
             The peaks  representing  2,3,7,8-TCDD, and the  first and
             last eluting TCDD  isomers  must  be  labeled  and identified.]
12.2  Mass Spectometer  Performance
      12.2.1 The mass spectrometer must be operated  in  the electron
             (impact) ionization  mode.   Static  mass  resolution  of  at
             least 10,000  (10%  valley)  must  be  demonstrated before any
             analysis of a  set  of samples  is performed  (Section 12.2.2).
             Static resolution  checks must be performed at the  beginn-
             ing and at the end of  each 12-hour period  of  operation.
             However, it is recommended that a  visual  check (e.g., not
             documented) of the static  resolution be made  using the
             peak matching  unit before  and  after each analysis.
     12.2.2  Chromatography time for TCDD may exceed the long-term
             mass stability of  the mass spectrometer; therefore, mass
             drift correction is mandatory.   A reference compound
             (high boiling perfluorokerosene [PFK] is recommended)
             is  introduced into the mass spectrometer.  An acceptable
             lock mass  ion at any mass between m/z 250 and m/z 334
             (m/z 318.979 from PFK  is  recommended) must be used to
             monitor and correct mass  drifts.
     [NOTE:  Excessive  PFK may cause background noise problems and
             contamination of the source, resulting in an  increase in
             "downtime" for  source  cleaning.  Using  a PFK molecular
             leak, tune the  instrument to meet the minimum required
             mass  resolution of  10,000 (10%  valley) at m/z 254.986
             (or any other mass  reasonably  close to m/z 259).  Cali-
             brate the  voltage sweep at least across the  mass  range
             m/z 259 to m/z  344  and verify  that m/z  330.979 from  PFK
             (or any other mass  close  to m/z 334)   is measured within
             ^5 ppm  (i.e.,  1.7 mmu).   Document the  mass resolution
             by recording  the  peak  profile  of  the PFK  reference peak
             m/z 318.979 (or any other reference  peak  at  a mass close
             to m/z  320/322).  The  format of the  peak  profile  represen-
             tation  must allow manual  determination of the resolution;

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                             T09-22
              i.e.,  the horizontal  axis  must  be  a  calibrated  mass
              scale  (mmu or ppm per division).   The  result  of the
              peak width measurement (performed  at 5 percent  of  the
              maximum)  must appear  on  the  hard copy  and  cannot exceed
              31.9 mmu  or 100 ppm.]
12.3  Initial  Calibration
      Intitial  calibration is required before any  samples are analyzed
      for 2,3,7,8-TCDD.  Initial  calibration  is  also required if any
      routine  calibration does  not  meet  the required criteria listed
      in  Section  12.6.
      12.3.1   All  concentration calibration solutions  listed  in  Table 1
              must be utilized  for  the initial calibration.
      12.3.2   Tune the  instrument with PFK as described  in
              Section 12.2.2.
      12.3.3   Inject 2  uL of  the  column  performance  check solution
              (Section  8.33)  and  acquire SIM  mass  spectral data  for m/z
              258.930,  319.897, 321.894, 331.937,  and  333.934 within
              a total cycle time  of 
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               T09-23
12.3.4.2   Acquire SIM data for the following  selected
           characteristic  ions:
                m/z          Compound
              258.930    TCDD - COC1
              319.897    unlabeled TCDD
              321.894    unlabeled TCDD
              331.937    13C12-2,3,7,8-TCDD,
                         13C12-1,2,3,4-TCDD
              333.934    13C12-2,3,7,8-TCDD,
                         13C12-1,2,3,4-TCDD
12.3.4.3   The ratio of intergrated ion current for m/z
           319.897 to m/z 321.894 for 2,3,7,8-TCDD must
           be between 0.67 and 0.87 (+13%).
12.3.4.4   The ratio of integrated ion current for m/z
           331.937 to m/z 333.934 for 13C12-2,3,7,8-TCDD
           and 13C12-1,2.3,4-TCDD must be between 0.67
           and 0.87.
12.3.4.5   Calculate the relative response factor for
           unlabeled 2,3,7,8-TCDD [RRF(I)] relative to
           13C12-2S3,758-TCDD  and for labeled 13C12-
           2,3,7,8-TCDD [RRF(II)] relative to 13C12-
           1,2,3,4-TCDD as follows:
                                     A» n
                                  Y    ^T ^
                   RRF(I) = ___	

                                QX  * AIS
                   RRF(II)-
                                      ARS

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                              T09-24
      where:

              Ax  =  sum of the integrated abundances of m/z 319.897
                     and m/z 321.894 for unlabeled 2,3,7,8,-TCDD.
                  =  sum of the integrated abundances of m/z 331.937
                     and m/z 333.934 for 13C12-2,3,7,8-TCDD.
                     sum of the integrated abundances for m/z 331.937
                     and m/z 333.934 for 13C12-1,2,3,4-TCDD.
              QJS =  quantity (pg) of 13C12-2,3,7,8-TCDD injected.
              QRS =  quantity (pg) of 13C12-1,2,3,4-TCDD injected.
              Qx  =  quantity (pg) of unlabeled 2,3,7,8-TCDD injected.
12.4  Criteria for Acceptable Calibration
      The criteria listed  below for acceptable calibration must  be met
      before analysis of any sample is  performed.
      12.4.1   The percent  relative standard deviation  (RSD)  for the
               response  factors  from each  of the triplicate  analyses
               for both  unlabeled  and 13C12-2,3S7,8-TCDD must be less
               than ±20%.
      12.4.2   The variation of  the five mean RRFs for  unlabeled
               2,3,7,8-TCDD  obtained from  the triplicate analyses
               must be less  than _+20% RSD.
      12.4.4   SIM traces for  13C12-2,3,7,8-TCDD must present a
               signal-to-noise ratio _>10 for 333.934.
      12.4.5   Isotopic  ratios  (Sections 12.3.4.3 and 12.3.4.4) must
               be  within the allowed  range.
      [NOTE:    If  the criteria for  acceptable calibration listed in
               Sections  12.4.1 and  12.4.2 have been met, the RRF can
              be  considered independent of the analyte quantity for
              the calibration concentration range.  The mean RRF
              from five triplicate determinations for unlabeled
              2.3,7,8-TCDD and for 13Cl22,3,7,8-TCDD will be used for
              all calculations until routine calibration criteria
              (Section 12.6) are no longer met.   At  such time, new
              mean RRFs will be calculated from a new set of five
              triplicate determinations.]

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                                 T09-25
     12.5  Routine Calibration
          Routine calibration must be performed at the beginning of each
          12-hour period after successful mass resolution and GC column
          performance check runs.
          12.5.1  Inject 2 uL of the concentration calibration solution
                  (Section 8.32) that contains 5.0 pg/uL of unlabeled
                  2,3,7,8-TCDD, 10.0 pg/uL of 13C12-2,3,7,8-TCDD, and 5.0
                  pg/uL 13C12-1,2,3,4-TCDD.  Using the same GC/MS/DS
                  conditions as in Sections 12.1, 12.2, and 12.3, deter-
                  mine and document acceptable calibration as provided
                  in Section 12.6.
     12.6  Criteria  for Acceptable Routine Calibration
          The  following criteria must be met before further analysis is
          performed.   If these criteria are not met, corrective action
          must be taken and the instrument must be recalibrated.
          12.6.1  The measured RRF for unlabeled 2,3,7,8-TCDD must be
                  within +20 percent of the mean values established
                  (Section 12.3.4.5) by triplicate analyses of concen-
                  tration calibration solutions.
          12.6.2  The measured RRF for 13Cl2-2,3,7,8-TCDD must be within
                  +20 percent of the mean value established by triplicate
                  analyses of concentration calibration solutions
                  (Section 12.3.4.5).
          12.6.3  Isotopic ratios  (Sections 12.3.4.3 and 12.3.4.4) must be
                  within the allowed range.
           12.6.4  If one of the above criteria  is not  satisfied, a  second
                  attempt can be made before repeating the entire initial-
                  ization process  (Section  12.3).
          [NOTE:  An initial calibration must be carried out  whenever  any
                  HRCC  solution is replaced.]
13.  Analytical Procedures
     13.1  Remove  the sample extract  or blank from storage, allow it  to
          warm to ambient  laboratory temperature, and  add  5 uL  of recovery
           standard  solution.  With a stream of  dry,  purified  nitrogen,
           reduce  the extract/blank volume to 20 uL.

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                              T09-26
 13.2   Inject  a  2-uL  aliquot  of the extract  into the GC? which should
       be  operating under the  conditions previously used (Section 12.1)
       to  produce acceptable  results with the performance check
       solution.
 13.3   Acquire SIM data using  the same acquisition time and MS operating
       conditions previously used (Section 12.3.4) to determine the
       relative  response factors for the following selected characteristic
       ions:
                 m/z       Compound
               258.930     TCDD - COC1 (weak at detection  limit  level)
               319.897     unlabeled  TCDD
               321.894     unlabeled  TCDD
               331.937     13C12-2,3,7,8-TCDD,   13C]2-1,2,3,4-TCDD,
               333.934     13C12-2,3,7,8-TCDD,   13C12-1,2,3,4-TCDD,
13.4  Identification  Criteria
      13.4.1   The  retention time  (RT)  (at maximum  peak height) of
              the  sample component m/z 319.897  must be within  -1 to
              +3 seconds of the retention time  of  the peak  for the
              isotopically  labeled  internal  standard at m/z 331.937
              to attain a positive  identification  of 2,3.7,8-TCDD.
              Retention times  of other tentatively identified TCDDs
              must fall within the RT  window established by analyzing
              the column performance check solution (Section 12.1).
              Retention times  are required for  all chromatograms.
      13.4.2   The ion  current  responses for  m/z 258.930, 319.897
             and 321.894 must reach their maxima simultaneously
              (+1 scan), and all ion current intensities must be
             >2.5 times noise level for positive identification of
             a  TCDD.
      13.4.3  The integrated ion current at m/z 319.897 must be
             between 67 and 87 percent of the ion current  response
             at m/z 321.894.

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                                 T09-27
                                                          t
          13.4.4   The  integrated  ion current at m/z 331.937 must be
                  between  67  and  87 percent of the ion current response
                  at m/z  333.934.
          13.4.5   The  integrated  ion currents for m/z 331.937 and 333.934
                  must reach  their maxima  within +1 scan.
          13.4.6   The  recovery  of the  internal standard  13C12-2,3,7,8-
                  TCDD must  be  between 40  and 120 percent.
14.  Calculations
     14.1  Calculate the  concentration of  2,3,7,8-TCDD (or any other  TCDD
           isomer) using  the formula:
                        Cx  *
                               AIS •  V •  RRF(I)
     where:
            Cx  -  quantity (pg)  of unlabeled  2,3,7,8-TCDD  (or  any  other
                   unlabeled TCDD isomer)  present.
            AX  =  sum of the integrated  ion  abundances  determined  for m/z
                   319.897 and 321.894.
            AIS =  sum °f the integrated  ion  abundances  determined  for m/z
                   331.937 and 333.934 of 13Cl2-2,3,7,8-TCDD (IS  =  internal
                   standard).
            QIS =  quantity (pg)  of 13C12-2,3,7,8-TCDD added to the
                   sample before extraction (Qjs =  500 pg).
            V   =  volume (m3) of air sampled.
         RRF(I) =  Calculated mean relative response factor for unlabeled
                   2,3,7,8-TCDD relative  to 13C12-2,3,7,8-TCDD.  This value
                   represents the grand mean  of the RRF(I)s obtained in
                   Section 12.3.4.5.

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                               T09-28
  14.2  Calculate the recovery of the internal  standard 13C-,2-2. 3,7,8
        TCDD, measured in the sample extract,  using the formula:
                                  AIS '  QRS
         Internal standard,                          x 100
         percent recovery =
                              ARS  •  RRF(II)  •

where:
     and QlS = same definitions as above  (Section  14.1)
        ARS  = sum of the integrated  ion  abundances  determined  for m/z
               331.937 and 333.934 of 13C12-1,2,3,4-TCDD  (RS  =  recovery
               standard).
        QRS  = quantity (pg)  of 13C12-1,2,3,4-TCDD added  to the
               sample residue before  HRGC-HRMS  analysis  (QRS  =  500 pg).
     RRF(II) = Calculated mean relative response factor  for labeled ^Cip-
               2,3,7,8-TCDD.   This value  represents  the  grand mean of the
               RRF(II)s calculated in Section 12.3.4.5.
  14.3  Total  TCDD Concentration
        14.3.1  All  positively identified  isomers  of TCDD must  be
                within the RT window  and  meet all  identification
                criteria listed in Sections  13.4.2,  13.4.3, and 13.4.4.
                Use the expression in Section 14.1 to  calculate the
                concentrations of  the other  TCDD isomers, with  Cx  be-
                coming the concentration  of  any unlabeled TCDD  isomer.
  14.4  Estimated  Detection Limit
        14.4.1  For samples in which  no unlabeled  2,3,7,8-TCDD  was
                detected, calculate the estimated  minimum detectable
                concentration.  The background  area  is determined  by
                integrating the ion abundances  for m/z 319.897  and
                321.894 in the appropriate region  and  relating  that
                height area to an  estimated  concentration that  would
                produce that  product  area.   Use the  formula:
                                   (2.5)  •  (A  ) • (QIS)
                             CE =             x      15
                                    (AIS)  -  RRF(I)  •  (W)

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                             T09-29

where:
      CE  = estimated concentration  of unlabeled  2,3,7,8-TCDD required
            to produce Ax.
      Ax  = sum of integrated ion abundance for m/z 319.897 and 321.894
            in the same group of >25 scans used to measure AI$.
      AIS - sum of integrated ion abundance for the appropriate ion
            characteristic of the internal standard, m/z 331.937 and
            m/z 333.934.
      QIS, RRF(I). and V  retain the definitions previously stated in
      Section 14.1.  Alternatively, if peak height measurements are used
      for quantification, measure the estimated detection limit by the peak
      height of the  noise in the TCDD RT window.
 14.5  The  relative percent difference (RPD) is calculated as follows:
       RPD
                 Si  -  S2
            (Mean  Concentration)
Si - S2
Si + S2)/Z
       Si and S2 represent  sample and  duplicate  sample  results.
 14.6  The total sample volume (Vm)  is calculated  from  the  periodic
       flow readings (Magnehelic) taken in  Section 10.3.6 using  the
       following equation:

                              Q  *<>2  •" QN      T
                                             *
 where:
        V         = total sample volume (nr).
     Q  Qp  *'*• QN = flow rates determined at the beginning, end, and inter-
                    mediate points during sampling (L/minute).
        N         = number of data points averaged.
        T         = elapsed sampling time (minutes).

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                                   T09-30
      14.7   The concentration  of  compound  in the  sample  is calculated using
            the following  equation:
                                   x    298
                             _
                             760
273 +
      where:
             V$ = total sample volume (m3) at 25°C and 760 mm Hg pressure.
             Vm = total sample flow (m3) under ambient conditions.
             PA » ambient pressure (mm Hg).
             tA = ambient temperature (°C).
     14.8  The concentration of compound in the sample is calculated
           using the following equation:
                         A x V
     where:
                            x V
             CA = concentration (ug/m3)  of analyte in the sample.
             A  = calculated amount of material  determined by HRGC/HRMS.
             Vi = volume (uL)  of extract injected.
             VE = final  volume (mL) of extract.
             V$ = total  volume (m3) of air samples corrected  to  standard
                  conditions.
15.  Performance Criteria and  Quality Assurance
     This section summarizes required quality  assurance  (QA)  measures  and
     provides guidance concerning  performance  criteria that should  be
     achieved within  each laboratory.
     15.1  Standard Operating  Procedures (SOPs)
           15.1.1 Users  should generate SOPs  describing  the  following
                  activities  in their laboratory:  1) assembly,  calibra-
                  tion  and  operation of the sampling system  with make
                  and model of equipment  used; 2)  preparation, purifica-
                  tion,  storage,  and handling of  sampling cartridges and
                  filters;  3)  assembly,  calibration and  operation  of the
                  HRGC/HRMS system with make  and  model of equipment used;
                  4) all  aspects  of  data  recording and processing, in-
                  cluding lists of computer hardware and software  used.

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                            T09-31
      15.1.2   SOPs  should  provide  specific  stepwise  instructions and
              should  be  readily  available to  and  understood  by the
              laboratory personnel  conducting the work.
15.2  Process, Field, and  Solvent  Blanks
      15.2.1   One PUF cartridge  and filter  from each batch of
              approximately 20 should be  analyzed, without shipment
              to the field, for the compounds of interest to serve as
              process blank.
      15.2.2  During each sampling episode, at least one PUF cartridge
              and filter should be shipped to the field and returned,
              without drawing air through the sampler, to serve as a
              field  blank.
      15.2.3  During the  analysis of each batch  of  samples, at least
              one  solvent  process blank (all  steps  conducted but no
              PUF  cartridge or  filter  included)  should  be carried
              through the procedure  and analyzed.

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                     T09-32
                    TABLE 1
COMPOSITION OF CONCENTRATION CALIBRATION SOLUTIONS
Recovery
13C -1
L12-l,
HRCC1
HRCC2
HRCC3
HRCC4
HRCC5

Standards
2,3,4-TCDD
2.5 pg/uL
5.0 pg/uL
10.0 pg/uL
20.0 pg/uL
40.0 pg/uL

Analyte
2,3,7,8-TCDD
2.5 pg/uL
5.0 pg/uL
10.0 pg/uL
20.0 pg/uL
40.0 pg/uL
Sample Fortification Solution
-Internal Standard
13C12-2,3,7,8-TCDD
10.0 pg/uL
10.0 pg/uL
10.0 pg/uL
10.0 pg/uL
10.0 pg/uL

      5.0 pg/uL of 13C12-2,3,7,8-TCDD
      Recovery Standard Spiking Solution
         100 pg/uL 13C12-1,2,3,4-TCDD
     Field Blank Fortification Solutions
   A)  4.0 pg/uL of unlabeled 2,3,7,8-TCDD
   B)  5.0 pg/uL of unlabeled 1,2,3,4-TCDD

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                                  T09-33
                                 TABLE 2
                   RECOMMENDED GC OPERATING CONDITIONS
Column coating             SP-2330 (SP 2331)          CP-SIL 88
Film thickness             0.20 urn                    0.22 urn
Column dimensions          60 m x 0.24 mm             50 m x 0.22 mm
Helium linear velocity     28-29 cm/sec at 240°C      28-29 cm/sec at 240°C
Initial temperature        200°C                      190°C
Initial time               4 min                      3 min
Temperature program        200°C to 250°C at          190°C to 240°C at
                           4°C/min                    5°C/min

-------
LOWER CANISTER
     RETAINING SCREEN
                            GLASS CARTRIDGE AND

                            ADSORBENT
                                             FILTER HOLDER SUPPORT
FILTER HOLDER WITH

 SUPPORT SCREEN
                                                                          4" DIAMETER FILTER
                  SILICONE RUBBER

                     GASKET
                                                    FILTER RETAINING RING
                   o
                   l£>
                   I
                   u>
                   -p.
        SILICONE

        RUBBER

        GASKETS
                           FIGURE 1. SAMPLING HEAD

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                             T09-35
 Magnehelic
   Gauge
  0-100 in.
  Exhaust
   Duct
(6 in. x 10 ft)
                   Sampling
                     Head
                 (See Figure 2)
                                ^Pipe Fitting (1/2 in.)
                                 Venturi
                                                    Voltage Variator


                                                    Elapsed Time Meter
7-Day
Timer
           FIGURE 2. HIGH VOLUME AIR SAMPLER
                GENERAL METAL WORKS (MODEL PS-1)

-------
 Performed by


 Date/Time
Calibration Orifice


Manometer S/N
S/N
Ambient Temperature


Bar.  Press.
                                             °C


                                            _mm Hg
Sampler
S/N










Variac
Setting V










Timer OK?
Yes/No










Calibration Orifice
Data
Manometer,
in. H00










Flow Rate
scm/min'a/










Sampler
Venturi Data
Magnehelic,
in. H00










Flow Rate
s cm/mi n'")










% Difference Between
Calibration and Sample
Venturi Flow Rates










Comments










                                                                                                                I
                                                                                                               o»
                                                                                                               Ot
(a) From Calibration Tables for Calibration Orifice or Venturi Tube
(b) From Calibration Tables for Venturi Tube in each Hi-Vol unit.
                                 Date check by
                                                                                            Date
                              FIGURE 3. EXAMPLE SAMPLING DATA  SHEET

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                             T09-37
                  SODIUM SULFATE
                  ACIDIC ALUMINA (-6.0 g)
                  GLASS WOOL PLUG
     (a) ALUMINA COLUMN
                                        SULFURIC ACID ON SILICA GEL (- 4.0 g)
                                        SILICA GEL <- 1.0 g)
                                        SODIUM SULFATE/POTASSIUM CARBONATE 11:1»
                                         GLASS WOOL PLUG
                                  (b) SILICA GEL COLUMN
FIGURE 4. MULTILAYERED EXTRACT CLEANUP COLUMNS

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                                                        Revi sion 1.0
                                                        June, 1987
                            METHOD T010
   METHOD  FOR  THE  DETERMINATION OF  ORGANOCHLORINE PESTICIDES IN
 AMBIENT  AIR USING LOW  VOLUME  POLYURETHANE FOAM (PUF) SAMPLING WITH GAS
           CHROMATOGRAPHY/ELECTRON  CAPTURE DETECTOR  (GC/ECD)
1.   Scope

     1.1   This document describes a method  for  sampling  and  analysis of  a
           variety of organochlorine pesticides  in  ambient  air.   The procedure
           is based on the adsorption of  chemicals  from ambient  air on
           polyurethane foam (PUF) using  a low volume  sampler.
     1.2   The low volume PUF sampling procedure is applicable to multi.com-
           ponent atmospheres containing  organochlorine pesticide concentrations
           from 0.01 to 50 ug/m3 over 4-  to  24-hour sampling  periods.
           The detection limit will depend  on the nature  of the  analyte and
           the length of the sampling period.
     1.3   Specific compounds for which the  method has been employed  are
           listed in Table 1.  The analysis  methodology described in  this
           document is currently employed by laboratories using  EPA Method
           608.  The sampling methodology has been formulated to meet the
           needs of pesticide sampling in ambient air.
 2.   Applicable Documents
     2.1   ASTM Standards
               D1356 - Definitions  of Terms Related to Atmospheric
                      Sampling and  Analysis.
           D1605-60  - Standard Recommended Practices  for Sampling
                      Atmospheres  for  Analysis  of Gases and Vapors.
                E260  - Recommended  Practice for  General Gas Chroma-
                      tography  Procedures.
                E355  -  Practice  for Gas Chromatography Terms  and
                       Relationships.
      2.2    EPA Documents

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                                  T010-2
           2.2.1   Compendium of Methods for the Determination of Toxic
                   Organic Compounds in Ambient Air. EPA-600/4-84-041,
                   U.S. Environmental Protection Agency, Research Triangle
                   Park, NC, April 1984.
         -  2-2.2   Manual of Analytical Methods for Determination of Pesti-
                   cides in Humans and Environmental Standards. EPA-
                   600/8-80-038, U.S. Environmental Protection Agency,
                   Research Triangle Park, NC, July 1982.
           2.2.3   "Test Method 608, Organochlorine Pesticides and PCBs,"
                   in EPA-600/4-82-057, U. S.  Environmental  Protection
                   Agency, Cincinnati, Ohio,  July 1982.
           2.2.4   R. G. Lewis,  ASTM draft report on standard practice
                   for sampling  and  analysis  pesticides  and  polychlorinated
                   biphenyls in  indoor atmospheres, U. S. Environmental
                   Protection Agency, Research Triangle  Park, NC,  June 1987,

3.   Summary of Method
     3.1   A low volume (1  to 5  L/minute)  sampler is used to  collect  va-
           pors on  a  sorbent  cartridge  containing PUF.   Airborne  particles
           may also be collected,  but the  sampling  efficiency is  not  known.
     3.2   Pesticides are  extracted  from the sorbent  cartridge with 5%
           diethyl  ether in  hexane and  determined  by  gas-liquid chro-
           matography coupled with an electron  capture detector (ECD).
           For some organochlorine pesticides,  high performance liquid
           chromatography  (HPLC) coupled with  an  ultraviolet  (UV)  detector
           or electrochemical  detector may be  preferable.  This method
           describes  the use  of an electron capture detector.
     3.3   Interferences  resulting from analytes  having  similar retention
           times  during  gas-liquid chromatography are resolved by  improv-
           ing  the  resolution  or separation, such as  by  changing the
           chromatographic column or  operating  parameters, or  by frac-
           tionating  the sample by column chromatography.
     3.4   Sampling procedure  is also applicable to other pesticides
           which may  be determined by gas-liquid chromatography coupled
           with a nitrogen-phosphorus detector  (NPD), flame photometric
           detector (FPD), Hall electrolytic conductivity detector (HECD),
           or  a mass  spectrometer (MS).

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                                T010-3
4.   Significance

     4.1   Pesticide usage and environmental  distribution  are  common  to
           rural  and urban areas of the United  States.   The  application
           of pesticides can cause adverse health effects  to humans by
           contaminating soil, water, air, plants, and  animal  life.
     4.2   Many pesticides exhibit bioaccumulative, chronic  health effects;
           therefore, monitoring the presence of these  compounds  in ambient
           air is of great importance.
     4.3   Use of a portable, low volume PUF sampling system allows the
           user flexibility in locating the apparatus.   The  user can
           place the apparatus in a stationary or mobile location.
           The portable sampling apparatus may be positioned in a vertical
           or horizontal stationary location (if necessary,  accompanied
           with supporting structure).  Mobile positioning of the
           system can be accomplished by attaching the apparatus to a
           person to test air in the individual's breathing zone.
           Moreover, the PUF  cartridge used in this method provides for
           successful collection of most  pesticides.
 5.   Definitions

      Definitions  used in  this document  and  in  any  user-prepared Standard
      Operating Procedures  (SOPs) should be  consistent  with ASTM D1356,
      D1605-60, E260, and  E355.   All  abbreviations  and  symbols  are defined
      within  this  document  at  point  of  use.
      5.1    Sampling efficiency  (SE)  -  ability  of  the sampling  medium to trap
            vapors of interest.   %SE is  the  percentage  of  the  analyte of in-
            terest collected  and retained  by the sampling  medium when it is
            introduced as  a vapor in air or  nitrogen  into  the  air  sampler and
            the sampler-  is operated under  normal  conditions  for a  period of
            time  equal  to  or greater than  that  required for  the intended use.
      5.2   Retention efficiency (RE) - ability of sampling  medium to  retain
            a compound  added (spiked) to it  in  liquid solution.
            5.2.1   Static retention efficiency - ability  of the sampling
                    medium to retain the solution spike when the
                    sampling cartridge is stored under clean,  quiescent
                    conditions for the duration of the test  period.

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                                T010-4
           5.2.2   Dyjnami^retention efficiency - ab 111 ty of the sampl 1 ng
                   medium to retain the solution spike when air or nit-
                   rogen is drawn through the sampling cartridge under
                   normal operating conditions for the duration of the
                   test period.  The dynamic RE is normally equal  to or
                   less than the SE.
     5.3   Retention time (RT)  - time to elute a specific chemical  from
           a chromatographic column.  For a specific carrier gas flow rate,
           RT is measured from  the time the chemical  is injected into the
           gas stream until  it  appears  at the detector.
     5'4   Relative retention time (RRT) - a ratio of RTs for two  chemi-
           cals for the same chromatographic column  and carrier gas  flow
           rate, where the  denominator  represents  a  reference chemical.
6.   Interferences

     6.1   Any gas or liquid chromatographic separation of  complex mix-
           tures of organic  chemicals is subject to  serious  interference
           problems due to  coelution of  two  or more  compounds.   The  use
           of capillary or narrowbore columns with superior  resolution
           and/or two or more columns of different polarity  will
           frequently eliminate these problems.
     6.2   The electron capture detector responds  to  a wide  variety  of
           organic  compounds.   It  is  likely  that such compounds  will be
           encountered  as interferences  during 6C/ECD analysis.  The NPD,
           FPD,  and HECD detectors are element specific, but are still
           subject  to  interferences.  UV detectors for HPLC are  nearly
           universal, and the electrochemical detector may also respond to
           a  variety  of  chemicals.  Mass spectrometric analyses will gene-
           rally  provide  positive  identification of specific compounds.
     6.3   Certain  organochlorine  pesticides (£.£., chlordane) are complex
           mixtures of  individual compounds that can make difficult
           accurate quantification of a  particular formulation in a multiple
           component mixture.  Polychlorinated biphenyls (PCBs) may inter-
           fere with the determination of pesticides.

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                               T010-5
    6.4   Contamination of glassware and sampling  apparatus with traces
          of pesticides can be a major source of error,  particularly at
          lower analyte concentrations.  Careful attention to cleaning
          and handling procedures is required during all  steps of sampling
          and analysis to minimize this source of  error.
    6.5   The general approaches listed below should be  followed to
          minimize interferences.
          6.5.1   Polar compounds, including certain pesticides (£.£•.
                  organophosphorus and carbamate classes), can be removed
                  by column chromatography on alumina.  This sample clean-
                  up will  permit analysis of most organochlorine pesticides.
          6.5.2   PCBs may be  separated from other  organochlorine
                  pesticides  by column  chromatography on  silicic
                  acid.
          6.5.3   Many  pesticides  can  be  fractionated into  groups by  column
                  chromatography on  Florisil  (Floridin Corp.).

7.   Apparatus

     7.1   Continuous-flow sampling pump (Figure 1)  -  (DuPont Alpha-1
           Air Sampler,  E.I.  DuPont de Nemours & Co.,  Inc.,  Wilimington,
           DE,  19898, or equivalent).
     7.2   Sampling  cartridge (Figure 2) - constructed from a 20 mm (i.d.)
           x 10 cm borosilicate glass tube drawn down  to  a 7 mm (o.d.)
           open connection for attachment to the pump  via Tygon tubing
           (Norton Co., P.O.  Box 350, Akron, OH, 44309,  or equivalent).
           The cartridge can be fabricated inexpensively from glass by
           Kontes (P.O. Box 729,'Vlneland, NJ, 08360), or equivalent.
     7.3   Sorbent, polyurethane foam (PUF) - cut  into a cylinder, 22 mm
           in diameter and 7.6 cm long, fitted under slight compression
           inside the cartridge.  The PUF should be of the polyether type,
           (density No. 3014 or 0.0225 g/cm3) used  for furniture upholstery,
           pillows, and mattresses;  it may be obtained from Olympic Products
           Co. (Greensboro, NC), or  equivalent  source.  The PUF cylinders
           (plugs) should  be  slightly  larger in diameter than the internal
           diameter  of the cartridge.  They may be  cut by one of the
           following means:

-------
                            T010-6
                  With a high-speed  cutting tool, such as a motorized
                  cork borer.   Distilled water should be used to lub-
                  ricate the cutting tool.
                  With a hot wire  cutter.  Care should be exercised
                  to  prevent thermal degradation of the foam.
                  With scissors, while plugs are compressed between
                  the 22 mm  circular templates.
       Alternatively,  pre-extracted PUF plugs and glass cartridges
       may  be  obtained commercially (Supelco, Inc., Supelco Park,
       Bellefonte, PA, 16823, No.  2-0557, or equivalent).
 7.4    Gas  chromatograph (GC) with an electron capture detector (ECD)
       and  either  an  isothermally controlled or temperature-programmed
       heating oven.   The analytical  system should be complete with all
       required accessories  including syringes, analytical  columns,
       gases, detector,  and  strip chart recorder.   A data system is
       recommended for measuring peak heights.  Consult EPA Method 608
       for  additional   specifications.
 7.5    Gas  chromatographic column, such as 4- or 2-mm (i.d.)  x 183 cm
       borosilicate glass packed with 1.5% SP-2250 (Supelco,  Inc.)/1.95%
       SP-2401 (Supelco, Inc.)  on 100/120 mesh Supelcoport (Supelco,
       Inc.), 4% SE-30 (General  Electric, 50 Fordham Rd.,  Wilmington,  MA,
       01887, or equivalent)/6% OV-210  (Ohio Valley  Specialty  Chemical,
       115  Industry Rd., Marietta,  OH,  45750,  or equivalent) on  100/200
       mesh Gas Chrom  Q  (Alltec Assoc., Applied Science Labs,  2051
       Waukegan Rd, Deerfield,  IL,  60015, or equivalent),  3% OV-101
       (Ohio Valley Specialty Chemical  )  on UltraBond  (Ultra Scientific,
       1 Main St., Hope, RI,  02831, or  equivalent) and  3%  OV-1  (Ohio
       Valley Specialty Chemical)  on  80/100 mesh Chromosorb WHP
       (Manville,  Filtration, and  Materials,  P.O.  Box  5108, Denver
       CO, 80271,  or equivalent).   Capillary GC column, such as  0.32
      mm (i.d.)  x 30  m DB-5  (J&W  Scientific,  3871 Security Park Dr.,
      Rancho Cordova, CA, 95670,  or  equivalent) with  0.25 urn  film  thick-
      ness.  HPLC column, such  as  4.6  mm x 25  cm  Zorbax SIL (DuPont
      Co.,  Concord Plaza, Wilmington,  DE,  19898, or equivalent)  or
      u-Bondapak  C-18 (Millipore  Corp.,  80 Ashby Rd., Bedfore,  MA,
      01730, or  equivalent).
7.6   Microsyringes - 5 uL volume  or other appropriate sizes.

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                                  T010-7
8.   Reagents and Materials
     [Note:   For a detailed listing of various  other  items  required  for
     extract preparation,  cleanup,  and analysis,  consult  U.S.  Method 608
     which is provided in  Appendix  A of Method  TO-4  in  the  Compendium.]
     8.1   Round bottom flasks,  500 ml, I 24/40 joints.
     8.2   Soxhlet extractors,  300  ml, with reflux condensers.
     8.3   Kuderna-Danish  concentrator apparatus,  500 ml, with  Snyder
           columns.
     8.4   Graduated concentrator tubes, 10 ml, with  J  19/22  stoppers
           (Kontes, P.O. Box 729, Vineland, NJ, 08360,  Cat. No.  K-570050,
           size 1025, or equivalent).
     8.5   Graduated concentrator tubes, 1 mL,  with  I 14/20 stoppers
           (Kontes, Vineland, NJ, Cat. No. K-570050,  size 0124,  or
           equivalent).
     8.6   TFE fluorocarbon tape, 1/2 in.
     8.7   Filter tubes, size 40 mm (i.d.) x 80 mm,  (Corning  Glass Works,
           Science Products, Houghton  Park, AB-1,  Corning,  NY,  14831, Cat.
           No. 9480, or equivalent).
     8.8   Serum vials, 1  ml and 5  mL, fitted with caps lined  with TFE
           fluorocarbon.
     8.9   Pasteur pipettes, 9  in.
    8.10   Glass wool fired at  500°C.
    8.11   Boiling chips fired  at 500°C.
    8.12   Forceps, stainless steel, 12 in.
    8.13   Gloves, latex or precleaned (5% ether/hexane Soxhlet  extracted)
           cotton.
    8.14   Steam bath.
    8.15   Heating mantles, 500  mL.
    8.16   Analytical evaporator, nitrogen blow-down  (N-EvapCii),  Organomation
           Assoc., P.O. Box 159, South Berlin,  MA, 01549, or  equivalent).
    8.17   Acetone, pesticide quality.
    8.18   n-Hexane, pesticide  quality.
    8.19   Diethyl ether preserved  with 2% ethanol (Mallinckrodt,  Inc.,
           Science Products Division,  P.O. Box  5840,  St.  Louis,  MO,  63134,
           Cat. No. 0850,  or equivalent).
    8.20   Sodium sulfate, anhydrous analytical grade.
    8.21   Alumina, activity grade  IV, 100/200  mesh.

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                             T010-8
 8.22  Glass chronatographic  column  (2 mm i.d. x 15 cm long).
 8.23  Soxhlet  extraction  system, including Soxhlet extractors
       (500  and  300 ml), variable voltage transformers, and
       cooling  water  source.
 8.24  Vacuum oven connected  to water aspirator.
 8.25  Die.
 8.26  Ice chest.
 8.27  Silicic  acid,  pesticide quality.
 8.28  Octachloronaphthalene  (OCN), research grade, (Ultra Scien-
       tific, Inc., 1 Main St., Hope, RI, 02831, or equivalent).
 8.29   Florisil  (Floridin Corp.).
 Assembly and Calibration of Sampling System
 9.1    Description of Sampling Apparatus
       9.1.1   The entire sampling system is diagrammed in Figure 1.
              This apparatus was developed  to  operate at  a rate of
              1-5 L/minute and is used  by U.S.  EPA for low volume
              sampling  of  ambient air.   The method writeup presents
              the use of this device.
      9.1.2   The sampling module (Figure 2) consists of  a glass
              sampling  cartridge  in which the PUF  plug is retained.
9.2   Calibration of  Sampling System
      9.2.1    Air flow  through the  sampling  system is calibrated  by
             the assembly shown  in  Figure  3.  The air sampler  must
              be calibrated  in the  laboratory before  and  after  each
             sample  collection period,  using the  procedure described
             below.
      9.2.2   For accurate calibration,  attach the sampling cartridge
             in-line during  calibration.   Vinyl bubble tubing  (Fisher
             Scientific,  711 Forbes Ave.,  Pittsburgh, PA,  15219,  Cat.
             No. 14-170-132,  or  equivalent) or other means (£.£.,
             rubber  stopper  or glass joint) may be used  to connect
             the large end of the cartridge to the calibration  system.
             Refer to ASTM Standard Practice D3686,  Annex A2 or
             Standard Practice D4185, Annex Al for procedures to
             calibrate small  volume air pumps.

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                                  T010-9

10.  Preparation  of Sampling (PUF)  Cartridges

     10.1  The PUF adsorbent is white and yellows  upon  exposure to  light.
     10.2  For initial  cleanup and quality  assurance  purposes, the  PUF
           plug is placed in a Soxhlet extractor  and  extracted with ace-
           tone for 14 to 24 hours at 4 to  6  cycles  per hour  (If commer-
           cially pre-extracted PUF plugs  are used,  extraction with ace-
           tone is not required.).  This  procedure is followed by a 16-hour
           Soxhlet extraction with 5% diethyl  ether in  n-hexane.  When
           cartridges are reused, 5% ether  in n-hexane  can  be used  as the
           cleanup solvent.
     10.3  The extracted PUF is placed in a vacuum oven connected to a
           water aspirator and dried at room temperature for  2 to 4 hours
           (until no solvent odor is detected).  The clean  PUF  is  placed  in
           labeled glass sampling cartridges using gloves and forceps.   The
           cartridges are wrapped with hexane-rinsed aluminum foil  and
           placed in glass jars fitted with TFE fluorocarbon-lined  caps.
           The foil wrapping may also be marked for identification  using
           a  blunt probe.
     10.4  At least one  assembled cartridge from each batch should  be an-
           alyzed as a laboratory blank before any samples  are analyzed.
           A  blank level of  <10 ng/plug for single component compounds  is
           considered to be  acceptable.  For multiple component mixtures,
           the blank level  should  be  <100  ng/plug.
 11.  Sampling
     11.1  After the  sampling  system  has been  assembled  and  calibrated as
           per Section 9,  it can  be  used to collect  air  samples as described
           below.
     11.2  The prepared  sample cartridges  should  be  used within 30 days of
           loading  and should be  handled only  with  latex or  precleaned
           cotton gloves.
      11.3  The clean sample cartridge is carefully  removed from the alumi-
            num foil  wrapping (the foil  is  returned  to  jars for later use)
            and attached  to the pump  with flexible tubing.  The sampling
            assembly is  positioned with the intake downward or horizontally.
            The sampler is  located in an  unobstructed area  at least 30 cm

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                               T010-10
           from any obstacle to air flow.  The PUF cartridge intake is
           positioned 1 to 2 m above ground level.  Cartridge height above
           ground is recorded on the Sampling Data Form shown in Figure 4.
     11.4  After the PUF cartridge is correctly inserted and positioned,
           the power switch is turned on and the sampling begins.   The
           elapsed time meter is activated and the start time is recorded.
           The pumps are checked during the sampling  process and any
           abnormal  conditions discovered are recorded  on the data  sheet.
           Ambient temperatures and barometric pressures are measured  and
           recorded periodically during the sampling  procedure.
     11.5  At the end of the desired sampling period, the power  is  turned
           off and the PUF cartridges are wrapped  with  the original  alumi-
           num foil  and placed in sealed, labeled  containers for transport
           back to the laboratory.   At least one field  blank is  returned
           to the laboratory with each group of samples.   A field blank
           is treated exactly like  a sample except that  no air is drawn
           through the cartridge.   Samples are stored at -10°C or below
           until  analyzed.
12.  Sample Preparation,  Cleanup, and Analysis
     [Note: Sample preparation should be preformed under a properly
            ventilated  hood.]
     12.1  Sample  Preparation
           12.1.1  All  samples should be extracted within  1  week after
                  col lection.
           12.1.2  All  glassware  is  washed  with a  suitable detergent;
                  rinsed with  deionized water,  acetone, and  hexane;
                  rinsed again with deionized  water; and  fired  in an
                  oven  (450°C).
           12.1.3  Sample extraction efficiency  is determined by spik-
                  ing the  samples with  a  known  solution.  Octachloro-
                  naphthalene  (OCN)  is  an  appropriate standard to use
                  for pesticide  analysis  using  GC/ECD techniques.  The
                  spiking  solution  is  prepared  by dissolving 10 mg of
                  OCN in 10 ml of 10%  acetone  in  n-hexane, followed by
                  serial dilution with  n-hexane to achieve a final
                  concentration of  1 ug/mL.

-------
                    T010-11
12.1.4  The extracting  solution (5%  ether/hexane)  is  prepared
        by mixing 1900  mL of freshly opened  hexane and  100  ml
        of freshly opened ethyl  ether (preserved with ethanol)
        to a flask.
12.1.5  All clean glassware, forceps, and  other equipment to
        be used are placed on rinsed (5% ether/hexane)  aluminum
        foil until use.  The forceps are also rinsed  with 5%
        ether/hexane.  The condensing towers are rinsed with
        5% ether/hexane and 300 ml are added to a  500 ml round
        bottom boiling  flask.
12.1.6  Using precleaned (£.£., 5% ether/hexane Soxhlet extracted)
        cotton gloves,  the PDF cartridges  are removed from the
        sealed container and the PDF is placed into a 300
        ml Soxhlet extractor using prerinsed forceps.
12.1.7  Before extraction begins, 100 uL of the OCN solution
        are added directly to the top of the PUF plug.   Addition
        of the standard demonstrates extraction efficiency of the
        Soxhlet procedure.  [Note:   Incorporating  a known concen-
        tration of the solution onto the sample provides a quality
        assurance  check to determine recovery efficiency of the
        extraction and analytical processes.]
12.1.8  The Soxhlet  extractor is then connected to the 500 ml
        boiling flask  and condenser.  The glass joints of the
        assembly  are wet with 5% ether/hexane to  ensure  a tight
        seal  between the fittings.   If necessary, the  PUF plug
        can be adjusted  using forceps to wedge it midway along
        the length of  the siphon.   The  above procedure should
        be followed  for  all  samples, with the  inclusion  of a
        blank control  sample.
 12.1.9  The water flow to the  condenser towers of  the  Soxhlet
        extraction assembly  is  checked  and  the heating unit is
        turned on.  As the  samples  boil, the Soxhlet extractors
        are inspected  to ensure that they are  filling  and  siphon-
        ing properly (4  to  6 cycles/hour).   Samples  should cycle
        for a minimum  of 16 hours.

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                             T010-12
       12.1.10 At the end  of  the  extracting process, the heating units
               are turned  off and the samples are cooled to room temper-
               ature.
       12.1.11 The extracts are concentrated to a 5 mL solution using a
               Kuderna-Danish (K-D) apparatus.  The K-D is set up and
               assembled with concentrator tubes.  This assembly is
               rinsed.  The lower end of the filter tube is packed with
               glass  wool  and filled with sodium sulfate to a depth of
               40  mm.  The filter tube is placed in the neck of the K-D.
               The Soxhlet extractors and boiling flasks are carefully
               removed from the condenser towers and the remaining sol-
               vent is drained into each boiling flask.  Sample extract
               is  carefully poured through the filter tube into the K-D.
               Each boiling flask is rinsed three times by swirling hex-
               ane along the  sides.   Once the  sample has drained,  the
               filter tube is rinsed down with hexane.   Each Synder column
               is  attached to the K-D and rinsed to wet the joint  for a
               tight  seal.  The complete K-D apparatus  is placed on a
               steam bath and the sample is evaporated  to approximately
               5 mL.  The sample is  removed from the steam  bath and
               allowed to cool.   Each  Synder column  is  rinsed  with  a
              minimum of hexane.  Sample volume is  adjusted to 10  ml
               in a concentrator tube,  which is  then closed with a  glass
              stopper and sealed  with  TFE fluorocarbon tape.   Alterna-
              tively, the sample  may  be quantitatively transferred (with
              concentrator tube rinsing)  to prescored  vials and brought
              up to final  volume.   Concentrated  extracts are  stored
              at -10°C until  analyzed.   Analysis  should  occur  no later
              than two weeks  after  sample  extraction.
12.2  Sample Cleanup
      12.2.1  If only organochlorine pesticides are sought, an  alumina
              cleanup procedure is  appropriate.   Before cleanup, the
              sample  extract  is carefully  reduced to 1 ml  using a
              gentle  stream of  clean nitrogen.
      12.2.2  A glass chromatographic column (2 mm  i.d. x  15 cm long)
              is packed with  alumina, activity  grade IV, and rinsed with
              approximately 20 ml of n-hexane.  The concentrated sample

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                            T010-13
              extract is placed on the column  and  eluted with  10 ml  of
              n-hexane at a rate of 0.5 mL/minute.   The  eluate volume
              is adjusted to exactly 10 mL and analyzed  as  per 12.3.
      12.2.3  If other pesticides are sought,  alternate  cleanup pro-
              cedures may be required (e^.£., Florisil).  EPA Method 608
              identifies appropriate cleanup procedures.
12.3  Sample Analysis
      12.3.1  Organochlorine pesticides and many nonchlorinated pesti-
              cides are responsive to electron capture detection
              (Table 1).  Most of these compounds  can be determined  at
              concentrations of 1 to 50 ng/mL  by 6C/ECD.
      12.3.2  An appropriate GC column is  selected  for analysis of the
              extract.  (For example, 4 mm i.d. x  183 cm glass, packed
              with 1.5% SP-2250/1.95% SP-2401  on 100/120 mesh  Supelo-
              port, 200°C isothermal, with 5%  methane/95% argon carrier
              gas at 65 to 85 mL/min).  A  chromatogram showing a mix-
              ture containing single component pesticides determined
              by GC/ECD using a packed column  is shown in Figure 5.
              A table of corresponding chromatographic characteristics
              follows in Figure 6.
      12.3.3  A standard solution is prepared  from  reference materials
              of known purity.   Standards  of organochlorine pesticides
              may be obtained from the National Bureau of Standards
              and from the U.S. EPA.
      12.3.4  Stock standard solutions (1.00 ug/uL)  are prepared by
              dissolving approximately 10  milligrams of pure material
              in isooctane and  diluting to volume  in a 10 mL volu-
              metric flask.   Larger volumes can be  used at the con-
              venience of the analyst.  If compound  purity  is  cer-
              tified at 96%  or  greater, the weight  can be used with-
              out correction to calculate  the  concentration of the
              stock standard.  Commerically prepared stock standards
              may be used at any concentration if they are certified
              by the manufacturer or an independent  source.
      12.3.5  The prepared stock standard  solutions  are transferred
              to Teflon-sealed  screw-capped bottles and stored  at -10°C
              for no longer  than six months.   The standard solutions
              should be inspected frequently for signs of degradation

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                      T010-14
        or evaporation (especially before preparing calibration
        standards from them).  [Note:  Quality control  check
        standards used to determine accuracy of the calibration
        standards are available from the U.S. Environmental
        Protection Agency, Environmental Monitoring and Support
        Laboratory, Cincinnati, Ohio 45268.]
12.3.6  The standard solutions of the various compounds of
        interest are used to determine relative retention
        times (RRTs) to an internal  standard such  as j3,j3'-DDE,
        aldrin, or OCN.
12.3.7  Before analysis,  the GC column is made sensitive to  the
        pesticide samples by injecting a standard  pesticide  solu-
        tion ten (10)  times more concentrated than the  stock
        standard solution.  Detector linearity is  then  determined
        by injecting standard solutions of three different concen-
        trations that  bracket the required range of analyses.
12.3.8  The GC system  is  calibrated  daily with a minimum of
        three injections  of calibrated standards.   Consult EPA
        Method 608,  Section 7 for a  detailed procedure  to
        calibrate the  gas  chromatograph.
12.3.9  If refrigerated,  the sample  extract  is removed  from  the
        cooling unit and  allowed  to  warm to  room temperature.   The
        sample extract  is  injected into the  GC for analysis  in
        an aliquot  of  approximately  2-6 uL using the solvent-
        flush technique (Ref.  D3687,  8.1.4.3-8.1.4.5).   The  actual
        volume injected is recorded  to the nearest  0.05  uL.  After
        GC injection, the  sample's response  from the strip chart
        is analyzed  by  measuring  peak  heights  or determining peak
        areas.  Ideally, the peak  heights  should be 20 to  80% of
        full  scale deflection.  Using  injections of 2 to 6 uL of
        each  calibration  standard, the peak  height  or area re-
        sponses  are  tabulated  against  the  mass  injected  (injec-
        tions  of 2,  4,  and  6 uL are  recommended).   If the  response
        (peak  height or area)  exceeds  the  linear range of  detec-
        tion,  the extract  is diluted  and  reanalyzed.

-------
                                T010-15
          12.3.10  Pesticide  mixtures  are quantified by comparison of the
                   total  heights or  areas of GC peaks with the correspond-
                   ing  peaks  in the  best-matching standard.  If both PCBs
                   and  organochlorine  pesticides are present in the same
                   sample,  column  chromatographic separation on silicic
                   acid is  used before GC analysis, according to ASTM
                   Standards, Vol. 14.01.   If  polar compounds that interfere
                   with GC/ECD analysis are present, column chromatographic
                   cleanup  on alumina  (activity grade IV) is used as per
                   Section  12.2.2.
          12.3.11  For  confirmation, a second  GC column is used such as
                   4% SE-30/6% OV-210  on 100/200 mesh Gas Chrom Q or 3%
                   OV-1 on  80/100 mesh Chromosorb WHP.  For improved re-
                   solution,  a capillary column is used such as 0.32 mm
                   (i.d.) x 30 m DB-5  with  0.25 urn film thickness.
          12.3.12  A chromatogram  of a mixture containing single component
                   pesticides determined by GC/ECD using a capillary column
                   is shown in Figure  7.  A table of the corresponding
                   chromatographic characteristics follows in Figure 8.
          12.3.13  Class separation  and improved specificity can be achieved
                   by column  chromatographic separation on Florisil as per
                   EPA  Method 608.   For improved specificity, a Hall
                   electrolytic conductivity detector operated in the
                   reductive  mode  may  be substituted for the electron
                   capture  detector.   Limits of detection will be reduced
                   by at least an  order of  magnitude, however.
13.  GC Calibration
     Appropriate calibration  procedures are identified  in EPA Method 608,
     Section 7.
14.  Calculations
     14.1  The concentration  of the  analyte in the extract solution is
           taken from a standard curve where peak height or area is
           plotted linearly against  concentration in nanograms per mini-
           liter (ng/mL).  If the  detector  response  is  known to be linear,
           a single point is  used  as a calculation constant.
     14.2  From the standard  curve,  determine  the ng of analyte standard
           equivalent to the  peak  height or area for a  particular compound.

-------
                            T010-16
14.3  Determine if the field blank  is contaminated.   Blank levels
      should not exceed 10 ng/sample  for organochlorine  pesticides
      or 100 ng/sample for other pesticides.   If  the  blank has been
      contaminated, the sampling series  must  be held  suspect.
14.4  Quantity of the compound  in the sample  (A)  is calculated
      using the following  equation:
                    A  =   1000
      where:

      A    =   total  amount  of  analyte  in the  sample  (ng).
      As   =   calculated  amount  of material (ng) injected onto the
              chromatograph based  on calibration curve  for  injected
              standards.
      Ve   =   final  volume  of  extract  (ml).
      V-j   =   volume of  extract  injected (uL).
   1000    =   factor for  converting microliters to milliliters.
14.5  The extraction efficiency  (EE) is determined from the  recovery
      of octachl oronaphthal ene (OCN) spike as follows:
                         EE(%)  =  S_ x 100
                                  Sa
      where:
              S  = amount of spike (ng) recovered.
              Sa = amount of spike (ng) added to plug.

14.6  The total  amount of nanograms found in  the sample is corrected
      for extraction efficiency  and laboratory blank as follows:


      where:
              AC = corrected amount of analyte in sample  (ng).
              A0 = amount of analyte in blank (ng).

-------
                            T010-17
14.7  The total  volume of air sampled  under ambient conditions  is
      determined using the following equation:

                                x   (T  x F)
                                  1000 L/m3
      where:
        Va   =  total  volume of air sampled (nr).
        T-J   =  length of sampling segment  (min)  between  flow  checks.
        F-J   =  average flow (L/min)  during sampling  segment.
14.8  The air volume is corrected to  25°  and 760  mm Hg  (STP) as
      follows:
                          /  Ph - Pw  \ -/29_8J<\
                          \  760 mm Hg/  \  t&  /
      where:
                                o
        Vs   =  volume of air (m )  at  standard  conditions.
        Va   =  total  volume of air sampled  (m3).
        Pb   =  average ambient barometric pressure (mm  Hg).
        Pw   =  vapor pressure of water (mm  Hg)  at  calibration  temperature.
        t/\   =  average ambient temperature  (K).
14.9  If the proper criteria for a  sample have  been met,  concentration
      of the compound in a cubic meter of air  is calculated as  follows:
                    ng/m3  = .  A,, x  100
                               "vf   "SET*)
      where:
      SE   =  sampling efficiency as determined  by  the procedure  out-
              lined in Section 15.
      If it is desired to convert the  air concentration  value to  parts
      per trillion (wt/wt) in dry air  at STP,  the following conversion
      is used:
                             ppt  =  1.205 ng/m3

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                              T010-18
        The  air concentration is converted to parts per trillion (v/v)  in
        air  at STP as follows:
                                        k45   /ng/m3 \
                                              I   MW  J
                                  pptv  =   24.
           where:

           MW   =   molecular  weight  of  the compound of  interest.
15.   Sampling and  Retention Efficiencies
 15.1  Before using this procedure,  the  user should  determine the  sam-
       pling efficiency for the  compound  of  interest.  The sampling
       efficiencies shown in Tables  2  and  3  were determined for approxi-
       mately 1  m3 of  air at about 25°C,  sampled at  3.8 L/min.  Sampling
       efficiencies for the pesticides shown  in Table 4 are for 24 hours
       at  3.8 L/min and 25°C.  For compounds  not listed, longer sampling
       times, different flow rates,  or other  air temperatures, the fol-
       lowing procedure may be used  to determine sampling efficiencies.
 15.2  SE  is  determined by  a modified impinger assembly attached to the
       sampler pump (Figure 9).  Clean PUF is placed in the pre-fliter
       location  and the inlet is attached to  a nitrogen line.   [Note:
       Nitrogen  should  be used instead of air to prevent oxidation of
       the compounds under  test.  The oxidation would not necessarily
       reflect what may  be  encountered during actual  sampling  and  may
       give misleading  sampling efficiencies.] PUF  plugs  (22 mm  x  7.6
       cm) are placed in the primary and  secondary  traps  and are atta-
       ched to the pump.
 15.3   A standard solution of the compound of interest  is  prepared
       in a volatile solvent (e_.£.,  hexane, pentane,  or benzene).   A
       small, accurately measured volume  (£.£.,  1 ml) of  the standard
       solution is placed into the modified midget  impinger.   The
       sampler pump is set at the rate  to  be used in  field  application
      and then activated.  Nitrogen  is drawn through the assembly  for
      a period of time equal to  or  exceeding that  intended for  field
      application.  After the  desired  sampling test  period, the PUF
      plugs  are  removed and analyzed separately as per Section  12.3.
15.4  The  impinger is  rinsed with hexane  or  another  suitable solvent
      and  quantitatively transferred to a  volumetric flask or concen-
      trator tube for  analysis.

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                            T010-19

15.5  The sampling efficiency (SE)  is  determined  using  the  following
      equation:
                     % SE   =      HT       x   100
      where:
                               WQ -
      Wj   =  amount of compound extracted  from the  primary  trap  (rig).
      W0   =  original  amount of compound  added to the  impinger  (ng).
      Wr   =  residue left  in the impinger  at  the end of  the test  (ng)
15.6  If material  is found  in the secondary trap, it is an indication
      that breakthrough has occurred.   The  addition  of  the amount  found
      in the secondary  trap,  W2, to Wi, will provide an indication of
      the overall  sampling  efficiency  of a  tandem-trap  sampling  system.
      The sum of Wj_, ^2 (if any)» and  wr must  eW^  (approximately +_
      10%) W0 or the test is  invalid.
15.7  If the compound of interest is not sufficiently volatile to  vapo-
      rize at room temperature,  the impinger may be  heated in a  water
      bath or other suitable  heater to a maximum of  50°C  to  aid  volati-
      lization.  If the compound of interest cannot  be  vaporized at
      50°C or without thermal degradation,  dynamic retention efficiency
      (REd) may be used to  estimate sampling efficiency.  Dynamic  re-
      tention efficiency is determined in  the  manner described in  15.80
      Table 5 lists those organochlorine pesticides  which dynamic  re-
      tention efficiencies  have  been determined.
15.8  A pair of PUF plugs is  spiked by slow, dropwise addition of  the
      standard solution to  one end of  each  plug. No more than 0.5 to
      1 ml of solution  should be used.  Amounts added to  each plug
      should be as nearly the same as  possible.  The plugs are allowed
      to dry for 2 hours in a clean, protected place (e_._g_.,  dessicator).
      One spiked plug is placed  in the primary trap  so  that  the  spiked
      end is at the intake  and one clean unspiked plug  is placed in the
      secondary trap.  The  other spiked plug is wrapped in hexane-rinsed
      aluminum foil and stored in a clean place for  the duration of the
      test (this is the static control plug, Section 15.9).   Prefiltered
      nitrogen or ambient air is drawn through the assembly  as per
      Section 15.3.  [Note:  Impinger may be discarded.]   Each PUF
      plug (spiked and  static control) is analyzed separately as per
      Section 12.3.

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                                 T010-20
     15.9  % REj) is calculated  as follows:
                                  Ml   x   100
                         % REd  =  ~Ro
           where:
           MI  =  amount  of compound  (ng)  recovered  from  primary  plug.
           W0  =  amount  of compound  (ng)  added  to primary  plug.

           If a residue,  W2,  is found  on  the  secondary  plug,  breakthrough
           has occurred.   The sum of Wj + W2  must equal W0, within  25%  or
           the test is  invalid.  For most compounds  tested  by this  proce-
           dure, % RE,j  values are generally less than % SE  values determined
           per Section  15.1.  The purpose of  the static RE^ determination
           is to establish any  loss or gain of analyte  unrelated  to the
           flow of nitrogen or  air through the PUF plug.
16.   Performance Criteria and Quality  Assurance
     This section summarizes  required  quality assurance (QA)  measures
     and provides guidance concerning  performance criteria  that should
     be achieved within each  laboratory.
     16.1  Standard Operating Procedures  (SOPs)
           16.1.1  Users  should generate  SOPs describing  the  following
                   activities accomplished in their  laboratory:
                   (1)   assembly, calibration, and operation  of the
                   sampling system, with  make and model of  equipment used;
                   (2)   preparation,  purification, storage, and
                   handling of  sampling cartridges,  (3) assembly,
                   calibration, and operation of the GC/ECD system,
                   with make and  model of equipment  used; and (4) all
                   aspects of data recording  and processing,  including
                   lists  of computer  hardware and  software  used.
           16.1.2  SOPs should  provide specific  stepwise  instructions  and
                   should be readily  available to, and  understood by,  the
                   laboratory personnel conducting the  work.

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                          T010-21

16.2  Process,  Field,  and  Solvent  Blanks

      16.2.1   One PUF  cartridge  from  each batch  of  approximately twenty
              should be  analyzed,  without shipment  to the field, for
              the compounds  of  interest to  serve  as a process blank.
      16.2.2   During each  sampling episode, at least one PUF cartridge
              should be  shipped  to the field  and  returned, without draw-
              ing air  through the  sampler,  to serve as a field blank.
      16.2.3   Before each  sampling episode, one  PUF plug from each
              batch of approximately  twenty should  be spiked with a
              known amount of the  standard  solution.  The spiked
              plug will  remain  in  a sealed  container and will not be
              used during  the sampling peroid.   The spiked plug  is
              extracted  and  analyzed  with the other samples.  This
              field spike  acts  as  a quality assurance check to
              determine  matrix  spike  recoveries  and to indicate  sample
              degradation.
      16.2.4   During the analysis  of  each batch  of  samples, at least
              one solvent  process  blank  (all  steps  conducted but no
              PUF cartridge  included) should  be  carried through  the
              procedure  and  analyzed.
      16.2.5   Blank levels should  not exceed  10  ng/sample for single
              components or 100 ng/sample for multiple component mix-
              tures (£•£., for  organochlorine pesticides).

16.3  Sampling Efficiency  and Spike Recovery

      16.3.1   Before using the  method for sample analysis, each  labo-
              ratory must  determine its  sampling efficiency  for  the
              component  of interest as  per  Section  15.
      16.3.2   The PUF  in the sampler  is  replaced with a hexane-extracted
              PUF.  The PUF is  spiked with  a  microgram level of  compounds
              of interest  by dropwise addition  of hexane  solutions of
              the compounds.  The  solvent is  allowed to evaporate.

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                          T010-22

      16.3.3  The sampling system is  activated  and  set  at the desired
              sampling flow rate.  The  sample flow  is monitored for
              24 hours.
      16.3.4  The PUF cartridge  is then removed  and  analyzed as per
              Section 12.3.
      16.3.5  A second sample, unspiked,  is  collected over the same
              time period  to account  for  any background levels of
              components  in  the  ambient air  matrix.
      16.3.6  In general,  analytical  recoveries  and  collection effi-
              ciencies of  75% are considered to  be  acceptable method
              performance.
      16.3.7  Replicate (at  least triplicate) determinations of col-
              lection efficiency should be made.  Relative standard
              deviations  for these replicate determinations of +15%
              or less are  considered  acceptable  performance.
      16.3.8  Blind  spiked samples should be included with sample sets
              periodically as a  check on  analytical  performance.
16.4  Method Precision and Accuracy
      16.4.1  Several  different  parameters involved  in both the samp-
              ling and analysis  steps of this method collectively
              determine the  accuracy  with which  each compound is detected,
              As the volume  of air sampled is increased, the sensitivity
              of detection increases  proportionately within limits set
              by (a) the  retention efficiency for each specific com-
              ponent trapped  on  the polyurethane foam plug, and (b) the
              background  interference associated with the analysis of
              each specific  component at  a given site sampled.  The
              accuracy of  detection of  samples recovered by extraction
              depends on  (a)  the inherent response  of the particular
              GC detector  used in the determinative  step, and (b) the
              extent to which the sample  is  concentrated for analysis.
              It is  the responsibility  of the analyst(s) performing the
              sampling and analysis steps to adjust  parameters so that
              the required detection  limits  can  be obtained.

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                         T010-23
      16.4.2  The  reproducibility of this method has been determined to
             range  from +5 to ^30%  (measured as the relative stan-
             dard deviation) when replicate sampling cartridges are
             used (N>5).  Sample recoveries for individual compounds
             generally fall within  the  range of 90 to  110%, but
             recoveries ranging from  75 to  115% are considered accept-
             able.   PUF alone may give  lower recoveries  for more  vola-
             tile compounds  (e_.£.,  those with  saturation vapor pres-
             sures  >10-3  mm Hg).   In  those  cases, another sorbent or
             a combination of  PUF and Tenax GC should  be employed.

16.5  Method Safety
      This procedure may  involve hazardous materials, operations,  and
      equipment.  This method  does  not purport  to  address all  of  the
      safety problems associated with  Us  use.   It is the users
      responsibility to consult and establish  appropriate safety  and
      health practices and determine the applicability  of regulatory
      limitations prior to the Implementation  of this procedure.
      This should be part of the users SOP manual.

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                       T010-24
          TABLE 1.  PESTICIDES DETERMINED BY
GAS CHROMATOGRAPHY/ELECTRON CAPTURE DETECTOR (GC/ECD)
 Aldrin
 BHC (a - and 0-Hexa-
   chlorocyclohexanes)
 Captan
 Chlordane, technical
 Chlorothalonll
 Chlorpyrifos
 2,4,-D esters
 £,£,-DDT
 £,£,-DDE
 Dieldrin
 Dlchlorvos (DDVP)
 Dicofol
 Endrin
 Endrin aldehyde
Folpet
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Lindane (y-BHC)
Methoxychlor
Mexacarbate
Mi rex
trans-Nonachlor
Oxychlordane
Pentachlorobenzene
Pentachlorophenol
Ronnel
2,4,5-Trichlorophenol

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                              T010-25
  TABLE 2.  SAMPLING EFFICIENCIES  FOR  SOME ORGANOCHLORINE PESTICIDES
Compound
a-Hexachlorocyclo-
hexane (a-BHC)
y-Hexachlorocyclo-
hexane (Lindane)
Hexachlorobenzene *
Chlordane, technical
£,£' -DDT
£,£'-DDE
Mi rex
Pentachlorobenzene *
Pentachlorophenol
2,4,5-Trichlorophenol
2,4-D Esters:
isopropyl
butyl
i sobutyl
i sooctyl
Quantity
Introduced, ug
0.005
0.05-1.0
0.5, 1.0
0.2
0.6, 1.2
0.2, 0.4
0.6, 1.2
1.0
1.0
t 1.0

0.5
0.5
0.5
0.5
,1 i • '-• "* !• —
Air
Volume,
m3
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9

3.6
3.6
3.6
3.6

Sampling
Efficiency, %
mean RSD n
115
91.5
94.5
84.0
97.5
102
85.9
94
107
108

92.0
82.0
79.0
>80*
•.,.- - i
8 6 '
8 5
8 5
11 8
21 12
11 12
22 7
12 5
16 5
3 5

5 12
10 11
20 12

*  Not vaporized.  Value base on %RE =  81.0 (RSD  =  10%,  n  =  6).
t  Semi volatile organochlorine pesticides.

-------
                                 T010-26


     TABLE 3.  SAMPLING EFFICIENCIES FOR ORGANOPHOSPHORUS PESTICIDES
                                                       Sampling
                          Quantity                    Efficiency, %
Compound                Introduced,b ug        mean       RSD
Dichlorvos (DDVP)
Ronnel
Chlorpyrifos
Diazinon3
Methyl parathion3
Ethyl parathion3
Malathion3
0.2
0.2
0.2
1.0
0.6
0.3
0.3
72.0
106
108
84.0
80.0
75.9
100C
13
8
9
18
19
15
—
2
12
12
18
18
18
—
a   Analyzed by gas chromatography with nitrogen phosphorus detector or
    flame photometric detector.

b   Air volume  =  0.9 m^.

c   Decomposed in generator; value based on %RE = 101
    (RDS = 7, n = 4).

-------
                                         T010-27
            TABLE  4    EXTRACTION  AND 24-HOUR SAMPLING EFFICIENCIES FOR VARIOUS
             IWSLt  <*.   tA.KHo  pESTICIDES  m RELATED COMPOUNDS
Compound
Chlorpyrifos
Pentachlorophenol
Chi or dan e
Lindane
DDVP
2,4-D methyl ester
Heptachlor
Aldrin
Dieldrin
Ronnel
Diazinon
trans-Nonachl or
Oxychlordane
«-BHC
 Chlorothalonil
 Heptachlor epoxide
 Extraction
 Efficiency, *%
 mean  RSD
83.3  11.5
84.0  22.6
95.0   7.1
96.0   6.9
88.3  20.2

99.0   1.7
97.7   4.0
95.0   7.0
80.3   19.5
72.0   21.8
97.7   4.0
100.0   0.0
 98.0   3.5
 90.3   8.4
100.0   0.0
                                                  Sampling  Efficiency, t %, at
                                                10 ng/m3     100 ng/m-3   1000 ng/m-3
                                                mean  RSD    mean  RSD   mean  RSD
83.7  18.0  92.7
66.7  42.2  52.3
96.0   1.4  74.0
91.7  11.6  93.0
51.0  53.7 106.0
75.3   6.8  58.0
97.3  13.6 103.0
90.7   5.5  94.0
82.7   7.6  85.0
74.7  12.1  60.7
63.7  18.9  41.3
96.7   4.2  101.7
95.3   9.5  94.3
86.7   13.7   97.0
 76.7    6.1   70.3
 95.3    5.5   97.7
15.1  83.7
36.2  66.7
 8.5  96.0
 2.6  91.7
 1.4  51.0
23.6  75.3
17.3  97.3
 2.6  90.7
11.5  82.7
15.5  74.7
26.6  63.7
15.3  96.7
  1.2  95.3
 18.2  86.7
  6.5  76.7
 14.2   95.3
18.0
42.2
 1.4
11.6
53.7
 6.8
13.6
 5.5
 7.6
12.2
19.9
 4.2
 9.5
 13.7
  6.1
  5.5
 * Mean values for one spike at 550 ng/plug
 t Mean values for three determinations.
                   and two spikes at 5500 ng/plug.

-------
                                           T012-28
              Table  5.   EXTRACTION  AND  24-HOUR  SAMPLING  EFFICIENCIES  FOR  VARIOUS
                               PESTICIDES AND RELATED COMPOUNDS
Compound
Dicofol
Captan
Methoxychlor
Folpet
Extraction Retention Efficiency, t %, at
Efficiency, *% 10 ng/m3 100 ng/m3 1000 ng/m3
mean RSD mean RSD mean RSD mean RSD
57-° 8-5 38.0 25.9 65.0 8.7 69.0
73-° 12-7 56.0 — 45.5 64.3 84.3 16.3
65'5 4-9 	 78.5 2.1
86-7 n-7 — — 78.0 — 93.0
*  Mean Values for one spike at 550 ng/plug and two spikes at 5500 ng/plug.
t  Mean Values for generally three determinations.

-------
                         T010-29
SAMPLING CARTRIDGE
    115V ADAPTER/
   CHARGER PLUG
         FIGURE 1.  LOW VOLUME AIR SAMPLER

-------
                 T010-30

            fm^^^^^Wmimi^^^^-
FIGURE 2. POLYURETHANE FOAM (PUF) SAMPLING
        CARTRIDGE

-------
                         T010-31
  FLOW RATE
METER (0-1 in H20)

  If
      FLOWRATE
        VALVE
         )
      x
    y
500 mL
BUBBLE
 TUBE
       AIR IN
           DISH WITH
        BUBBLE SOLUTION
                                PRESSURE DROP
                                METER (0-50 in H20)
r™ ____ --------
    VALVE
             I
                                                  PUMP
   FIGURE 3. CALIBRATION ASSEMBLY FOR AIR SAMPLER
             PUMP

-------
yiiH 	 . 	 Date PPrfnrmrrl hv

Sampler
S/N












Sampling
Location
I.D.












Height
above
Ground












PUF Cart.
No.












Samplin
Start











Period
Stop











Sampling
Time min.






















Pump Timer
hr. min.











Low flow
Indication
Yes Nn






















Comments











                                                                 o
                                                                 I—'
                                                                 o
                                                                 I
                                                                 CO
                                                                 ro
                                      Checked by_


                                      Date
FIGURE 4. LOW VOLUME PESTICIDE SAMPLING DATA FORM

-------
                        T010-33
                  OPERATING CONDITIONS
                  Column Type:   1.5% SP 2250/1.95% SP 2401,
                              V4" glass.
                  Temperature:   200°C isothermal.
                  Detector:      Electron Capture.
                  Carrier Gas:   5% Methane/95% Argon.
                  Flow Rate:    65 to 85 mL/min.
 Lindane
   Heptachlor

     Aldrin
              Dieldrin
                                          Dibutylchlorendate
                                                Methoxychlor
TIME
 FIGURE 5. CHROMATOGRAM SHOWING A MIXTURE OF
           SINGLE COMPONENT PESTICIDES DETERMINED BY
           GC/ECD USING A PACKED COLUMN

-------
                          T010-34
                    EXTERNAL STANDARD TABLE
             SINGLE COMPONENT PESTICIDE MIXTURE (5uL) ON
                       A PACKED COLUMN
RETENTION COMPOUND CONCENTRATION IN PG
TIME NAME ON COLUMN
2.77
3.37
4.03
8.90
10.72
14.63
24.87
26.82
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
p.p'-DDT
Di butyl chlorendate*
Methoxychlor
500
500
500
500
500
500
2500
2500
AREA/
HEIGHT
8.2
10.4
12.0
24.7
30.2
39.0
61.4
57.5
       Internal standard used for earlier pesticide detection.
FIGURE 6. CHROMATOGRAPHIC CHARACTERISTICS OF THE
         SINGLE COMPONENT PESTICIDE MIXTURE
         DETERMINED BY GC/ECD USING A
         PACKED COLUMN

-------
                           T010-35
           OPERATING CONDITIONS _
           Column Type:   DB-5 0.32 capillary,
                        0.25 urn film thickness
           Column Temperature Program:  90°C (4 min)/16°C per min to
                        154°C/4°C per min to 270°C.
           Detector:       Electron Capture
           Carrier Gas:     Helium at 1 mL/min.
           Make Up Gas:   5% Methane/95% Argon at 60 mL/min.
TIME
             Heptachlor
         Lindane
                               Dibutylchlorendate
                                    Methoxychlor
Aldrin  Endrjn
                            Dieldrin
FIGURE 7.  CHROMATOGRAM SHOWING A MIXTURE OF
            SINGLE COMPONENT PESTICIDES DETERMINED BY
            GC/ECD USING A CAPILLARY COLUMN

-------
                        T010-36
                 EXTERNAL STANDARD TABLE
          SINGLE COMPONENT PESTICIDE MIXTURE (2uL) ON
                  ON A CAPILLARY COLUMN
RETENTION
TIME
14.28
17.41
18.96
23.63
24.63
27.24
29.92
31.49
COMPOUND
NAME
CONCENTRATION
ON COLUMN
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
p.p'-DDT
Methoxychlor





Di butyl chl orendate*
IN PG
200
200
200
200
200
200
1000
1000
AREA/
HEIGHT
5.2
5.3
5.4
*f * ~
5.8
6.3
5.6
5.5
5.4
  * Internal standard used for earlier pesticide detection.
FIGURE 8. CHROMATOGRAPHIC CHARACTERISTICS OF THE
         SINGLE COMPONENT PESTICIDE MIXTURE
         DETERMINED BY GC/ECD USING A
         CAPILLARY COLUMN

-------
    AIR INLET
                                                   AIR TO PUMPING
                                                       SYSTEM
                     COLLECTION
                      MEDIUM
                                     COLLECTION
                                      MEDIUM
                                      BACK-UP
CD
I—1
o
GO
FIGURE 9. APPARATUS FOR DETERMINING SAMPLING
          EFFICIENCIES

-------

-------
                                                             Revision 1.0
                                                             June, 1987
                               METHOD T011
       METHOD FOR THE DETERMINATION OF FORMALDEHYDE IN AMBIENT AIR
        USING ADSORBENT CARTRIDGE FOLLOWED BY HIGH PERFORMANCE
                     LIQUID CHROMATOGRAPHY (HPLC)
1.   Scope
     1.1  This document describes a method for the determi nation of
          formaldehyde in ambient air utilizing solid adsorbent fol-
          lowed by high performance liquid chromatographic detection.
          Formaldehyde has been found to be a major promoter  in the
          formation of photochemical ozone.  In particular, short
          term exposure to formaldehyde and other specific aldehydes
          (acetaldehyde, acrolein, crotonaldehyde) is known to  cause
          irritation of the eyes, skin, and mucous membranes  of the
          upper respiratory tract.
     1.2  Compendium Method T05,  "Method For the Determination  of
          Aldehydes and Ketones in Ambient Air Using High Perform-
          ance Liquid Chromatography (HPLC)" involves drawing
          ambient air through  a midget impinger sampling train  con-
          taining 10 mL of 2N  HC1/0.05% 2,4-dinitrophenylhydrazine
          (DNPH) reagent.  Aldehydes and ketones readily  form a stable
          derivative with the  DNPH  reagent, and the DNPH  derivative
          is analyzed for aldehydes and ketones utilizing HPLC.
          Method T011 modifies the  sampling procedures  outlined in
          Method T05 by introducing a coated adsorbent  for  sampling
          formaldehyde.  This  current method is based  on  the  specific
          reaction of organic  carbonyl compounds  (aldehydes  and
          ketones) with DNPH-coated cartridges  in  the  presence of an
          acid to form stable  derivatives  according to  the  following
          equation:
                         N02                             N02
                                              R1
           \            /  \        H+       \       /\
            C = 0 + H2N-NH—^    NV- NQ2  	>-     C = N-NH—('     /—N02 + H2°
        CARBONYL GROUP      2.4-DINITROPHENYLHYDRAZINE        nMpl. npmx/AT,.,p     WATFR
     (ALDEHYDES AND KETONES)          (DNPH)               DNPH-DERIVATIVE     WATER
           where R  and  R'  are organic alkyl  or aromatic group (ketones) or
           either substituent is a hydrogen  (aldehydes).

-------
                           T011-2
      The  determination of formaldehyde from the DNPH-formaldehyde
      derivative is similar to Method T05 in incorporating HPLC.
      The  detection limits have been extended and other aldehydes
      and  ketones can be determined as outlined in Section 14.
 1.3   The  sampling method gives a time-weighted average (TWA) sample.
      It can be used for long-term (1-24 hr) sampling of ambient air
      where the concentration of formaldehyde is generally in the
      low  (1-20) ppb (v/v) or for short-term (5-60 min) sampling
      of source-impacted atmospheres where the concentration  of
      formaldehyde could reach the ppm (v/v) levels.
1.4  The sampling flow rate,  as described in this document,  is
     presently limited to about 1.5 L/min.   This  limitation  is
     principally due  to the  high pressure drop  across  the  DNPH-
     coated silica  gel  cartridges.   Because of  this, the  procedure  is
     not compatible with  pumps  used  in  personal sampling  equipments.
1.5  The method instructs  the user to purchase  Sep-PAK chromato-
     graphic  grade  silica  gel cartridges  (Waters Associates,
     34 Maple  St.,  Mil ford, MA  01757) and apply acidified  DNPH
     in situ to each cartridge  as part  of the user-prepared
     quality assurance  program  (1,2).   Commercially pre-coated  DNPH
     cartridges are also available.  [Caution:  Recent  studies
     have  indicated abnormally  high formaldehyde background
     levels in  commercially prepacked cartridges.  It  is advised
     that  three cartridges randomly selected from each production
     lot,  be analyzed for formaldehyde prior to use to determine
     acceptable levels.] Thermosorb/F cartridges (Thermedics,
     Inc., 470  Wildwood St., P.O. Box 2999, Woburn, MA, 01888-1799)
     can be purchased prepacked.  The cartridges are  1.5 cm ID x
     2 cm  long  polyethylene tubes with Luer®-type fittings on
     each end.  The adsorbent is composed of 60/80-mesh Florisil
     (magnesium silicate) coated with 2,4-dinitrophenylhydrazine.
     The adsorbent is  held in place  with 100 mesh  stainless
     steel screens at  each end.   The precoated cartridges  are
     used as received  and are discarded  after use. The cartridges
    are stored in glass culture tubes with polypropylene  caps
    and placed in cold storage  when  not in  use.

-------
                           T011-3
1.6  This method may involve hazardous materials,  operations,
     and equipments.  This method  does not  purport to  address
     all the safety problems associated with its use.   It is the
     responsibility of whoever uses this method to consult and
     establish appropriate safety  and health practices and deter-
     mine the applicability of regulatory limitations  prior to use.
Applicable Documents
2.1  ASTM Standards
         D1356 - Definition of Terms Relating to Atmospheric Sampling
                and Analysis
         E682  - Practice  for Liquid Chromatography Terms and
                Relationships
2.2  Other  Documents
         Existing  Procedures  (3-5)
         Ambient  Air Studies  (6-8)
         U.  S.  EPA Technical  Assistance Document (9)
         Indoor Air Studies  (10-11)
 Summary of Method
 3.1  A known volume of ambient air is drawn through a prepacked
      silica gel  cartridge coated  with acidified DNPH  at  a sampling
      rate of 500-1200 mL/min for  an appropriate period of time.
      Sampling rate and time are dependent  upon carbonyl  concentra-
      tion in the test atmosphere.
 3.2  After sampling, the sample cartridges are capped and placed in
      borosilicate glass culture tubes with polypropylene caps.
      The capped tubes are then placed in a friction-top can con-
      taining a pouch of charcoal  and  returned to the  laboratory
      for analysis.  Alternatively, the sample vials can be placed
      in a  styrofoam box with appropriate padding for shipment to
      the laboratory.  The cartridges  may either  be placed  in cold
      storage until analysis or immediately washed by gravity
      feed  elution  of  6 ml  of  acetonitrile  from a plastic  syringe
      reservoir to  a  graduated test tube or a  5 ml volumetric flask.
  3.3 The  eluate  is then  topped to  a  known  volume and  refrigerated
      until  analysis.
  3.4 The  DNPH-formaldehyde derivative is  determined  using isocratic
       reverse  phase HPLC  with  an  ultraviolet  (UV) absorption  detector
       operated  at 360 nm.

-------
                              T011-4
 3.5  A cartridge  blank  is  likewise desorbed  and  analyzed  as  per Sec-
      tion  3.4.
 3.6  Formaldehyde and other  carbonyl  compounds in the sample are  iden-
      tified  and quantified by comparison of  their retention times
      and peak  heights or peak areas with those of standard solutions.
 Significance
 4.1   Formaldehyde has been found to be a major promoter in the forma-
      tion  of photochemical ozone (12).  In particular, short term ex-
      posure  to formaldehyde  and other specific aldehydes  (acetaldehyde,
      acrolein, crotonaldehyde) is known to cause irritation of the
      eyes, skin,  and mucous  membranes of the upper respiratory tract
      (13).   Animal studies indicate that high concentrations can in-
      jure  the  lungs and other organs of the  body (14).  Formaldehyde
      may contribute to eye irritation and unpleasant odors that are
      common  annoyances in polluted atmospheres.
 4.2   Formaldehyde  emissions  result from incomplete combustion of hydro-
      carbons and  other organic materials.  The major emission sources
      appear  to be  vehicle exhaust, incineration of wastes, and burning
      of fuels (natural  gas,  fuel  oil, and coal).   In addition, signifi-
      cant  amounts  of atmospheric formaldehyde can result from photo-
      chemical reactions between reactive hydrocarbons and nitrogen
      oxides.  Moreover,  formaldehyde can react photochemically to pro-
      duce  other products,  including  ozone,  peroxides, and peroxyacetyl
      nitrate compounds.   Local sources of formaldehyde may include
     manufacturing and  other industrial  processes using  the chemical.
      In particular, formaldehyde  emissions  are associated with any
      industrial process  that  results  in  the pyrolysis of organic
     compounds  in air or oxygen.   This test method provides a means
     to determine concentrations  of  formaldehyde  and  other carbonyl
     compounds  in emissions sources  in various working environment
     and in ambient indoor  and outdoor atmospheres.
Definitions
5.1  Definitions  used  in this document and  in any user-prepared Stan-
     dard  Operating Procedures (SOPs)  should  be consistent with ASTM
     Methods  D1356 and E682.   All  abbreviations and  symbols within
     this  document are defined the first  time they are used.

-------
                                  T011-5
6.   Interferences
     6.1  This procedure has  been  written  specifically  for the  sampling
          and analysis of formaldehyde.   Interferences  in the method  are
         ' certain isomeric aldehydes  or  ketones  that  may be  unresolved by
          the HPLC system when analyzing  for other aldehydes and  ketones.
          Organic compounds that have the  same  retention time and signifi-
          cant absorbance at 360 nm as the DNPH  derivative of formaldehyde
          will interfere.  Such interferences can  often be overcome  by
          altering the separation  conditions (e.g., using  alternative HPLC
          columns or mobile phase  compositions).  However, other  aldehydes
          and ketones can be detected with a modification  of the  basic
          procedure.  In particular,  chromatographic conditions can  be
          optimized to separate acrolein,  acetone, and propionaldehyde
          and the following higher molecular weight aldehydes and ketones
          (within an analysis time of about one hour) by utilizing two
          Zorbax ODS columns in series under a  linear gradient  program:
                 Formaldehyde             Isovaleraldehyde
                 Acetaldehyde             Valeraldehyde
                 Acrolein                 o-Tolualdehyde
                 Acetone                  m-Tolualdehyde
                 Propionaldehyde          p-Tolualdehyde
                 Crotonaldehyde           Hexanaldehyde
                 Butyraldehyde            2,5-Dimethylbenzaldehyde
                 Benzaldehyde
          The  linear  gradient  program varies the mobile phase composition
          periodically  to  achieve maximum resolution of the C-3, C-4, and
          benzaldehyde  region  of the  chromatogram.   The following gradient
          program was  found  to be adequate  to achieve this  goal:  Upon
          sample injection,  linear gradient  from  60-75% acetonitrile/40-25%
          water  in  30 minutes,  linear gradient  from  75-100% acetonitrile/
          25-0%  water in 20  minutes,  hold at 100%  acetonitrile for 5 minutes,
          reverse  gradient to 60% acetonitrile/40% water in 1 minute, and
          maintain  isocratic at 60%  acetonitrile/40% water  for 15 minutes.

-------
                              T011-6
 6.2  Formaldehyde contamination  of  the  DNPH  reagent  is  a  frequently
      encountered problem.   The DNPH must  be  purified  by multiple
      recrystallizations  in  UV grade acetonitrile.  Recrystalliza-
      tion  is  accomplished at  40-60°C by slow evaporation  of  the
      solvent  to maximize crystal  size.  The  purified  DNPH crystals
      are stored under  UV grade acetonitrile  until use.  Impurity
      levels of  carbonyl compounds in the  DNPH are determined by HPLC
      prior to use and  should  be  less than 0.025 ug/mL.
 Apparatus

 7.1    Isocratic HPLC system consisting of a  mobile phase  reservoir;
       a high  pressure  pump; an injection  valve (automatic sampler
       with an optional 25-uL  loop injector); a Zorbax ODS (DuPont
       Instruments, Wilmington, DE),  or equivalent C-18, reverse phase
       (RP) column, or  equivalent (25  cm x 4.6 mm ID); a variable
       wavelength  UV detector  operating at 360 nm; and a data system
       or strip  chart recorder (Figure 1).
 7.2    Sampling  system  - capable of  accurately and precisely sampling
       100-1500  mL/min  of ambient air  (Figure 2).  The dry test meter
       may  not be  accurate at  flows  below 500 mL/min,  and should then
       be replaced by recorded flow  readings at the start,  finish,
       and  hourly during the collection.   The sample pump consists of
       a diaphragm or metal  bellows pump capable of extracting an air
       sample  between 500-1200 mL/min.  [Note:  A normal  pressure drop
      through the sample cartridge approaches 14 cm Hg at  a  sampling
       rate of 1.5 L/min.]
7.3   Stopwatch.
7.4   Friction-top metal  can  (e.g.,  1-gallon paint can)  or a styrofoam
      box with polyethlyene-air  bubble padding -  to hold sample vials.
7.5   Thermometer - to record ambient temperature.
7.6   Barometer (optional).
7.7   Suction  filtration apparatus - for filtering  HPLC  mobile  phase.
7.8   Volumetric flasks -  various sizes,  5-2000  mL.
7.9   Pipets  - various sizes,  1-50 mL.
7.10  Helium  purge line (optional) - for degassing  HPLC  mobile  phase.
7.11  Erlenmeyer flask, 1 L  -  for preparing  HPLC mobile  phase.

-------
                             T011-7
7.12  Graduated cylinder,  1 L -  for  preparing  HPLC  mobile  phase.
7.13  Syringe, 100-250 uL  - for  HPLC injection.
7.14  Sample vials.
7.15  Melting point apparatus.
7.16  Rotameters.
7.17  Calibrated syringes.
7.18  Special glass apparatus for rinsing, storing  and dispensing
      saturated DNPH stock reagent (Figure 3).
7.19  Mass flow meters and mass flow controllers for metering/setting
      air flow rate through sample cartridge of 500-1200 mL/min.  [Note:
      The mass flow controllers are necessary because cartridges
      have a  high  pressure drop and at maximum flow rates, the
      cartridge behaves like  a  "critical orifice."   Recent studies
      have shown that critical  flow orifices may be used for 24-hour
      sampling periods at  a maximum rate of 1 L/min for atmospheres
      not heavily  loaded with particulates without any problems.]
7.20  Positive displacement,  repetitive dispensing pipets (Lab-Indus-
      tries,  or  equivalent),  0-10 mL range.
7.21  Cartridge  drying manifold with multiple standard male Luer® con-
      nectors.
7.22  Liquid  syringes, 10  mL (polypropylene syringes  are  adequate) for
      preparing  DNPH-coated  cartridges.
7.23  Syringe rack -  made  of an aluminum  plate  (0.16  x 36 x 53  cm)
      with  adjustable legs on four  corners.   A  matrix (5  x 9) of cir-
      cular holes  of  diameter slightly  larger than the diameter of
      the 10-mL  syringes  was symetrically drilled  from the center of
      the plate  to enable batch processing of 45 cartridges for clean-
       ing,  coating, and/or sample  elution.
 7.24   Luer® fittings/plugs - to connect cartridges to sampling  system
      and to cap prepared cartridges.
 7.25   Hot plates,  beakers, flasks,  measuring  and disposable pipets,
       volumetric flasks,  etc. - used  in the purification  of DNPH.
 7.26   Borosilicate glass  culture tubes  (20 mm x 125 mm)  with  polypro-
       pylene screw caps  - used  to transport Sep-PAK coated  cartridges
       for field applications (Fisher Scientific,  Pittsburgh,  PA, or
       equivalent).
 7.27  Heated probe - necessary  when ambient temperature to be sampled
       is below 60°F to insure the effective collection of formaldehyde
       as a hydrazone.

-------
                           T011-8
7.28  Cartridge sampler - prepacked silica gel cartridge, Sep-PAK
      (Waters Associates, Mil ford, MA 01757, or equivalent) coated
      in situ with DNPH according to Section 9.
7.29  Polyethylene gloves - used to handle Sep-PAK silica gel  cart-
      ridges, best source.
Reagents and Materials
8.1   2,4-Dinitrophenylhydrazine (DNPH)- Aldrich Chemical or J.T. Baker,
      reagent grade or equivalent.  Recrystallize at least twice
      with UV grade acetonitrile before use.
8.2   Acetonitrile - UV grade, Burdick and Jackson "distilled-in-
      glass," or equivalent.
8.3   Deionized-distilled water - charcoal filtered.
8.4   Perchloric acid - analytical  grade, best source.
8.5   Hydrochloric acid - analytical  grade, best source.
8.6   Formaldehyde - analytical grade, best source.
8.7   Aldehydes and ketones, analytical  grade, best source - used
      for preparation of DNPH derivative standards (optional).
8.8   Ethanol or methanol  - analytical  grade, best source.
8.9   Sep-PAK silica gel  cartridge - Waters Associates,  34 Maple St.,
      Mil ford, MA, 01757,  or equivalent.
8.10  Nitrogen - high purity grade, best source.
8.11  Charcoal - granular, best source.
8.12  Helium - high purity grade, best source.
Preparation of Reagents and Cartridges
9.1  Purification of 2,4-Dinitrophenylhydrazine (DNPH)
     [Note:  This procedure should  be  performed under a  properly
     ventilated hood.]
     9.1.1   Prepare a supersaturated  solution of DNPH by boiling excess
            DNPH in 200 mL of acetonitrile for approximately one hour.
     9.1.2   After one hour,  remove  and transfer the supernatant to a
            covered beaker on a hot plate and allow gradual  cooling
            to 40-60°C.
     9.1.3   Maintain the solution at  this temperature (40-60°C) until
            95% of solvent has evaporated.

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                       T011-9
9.1.4  Decant solution to waste,  and  rinse  crystals  twice with
       three times their apparent volume  of acetonitrile.   [Note:
       Various health effects are resultant from the inhalation of
       acetonitrile.   At 500 ppm  in  air,  brief inhalation has pro-
       duced nose and throat irritation.  At 160 ppm, inhalation
       for 4 hours has caused flushing of the face  (2 hour  delay
       after exposure) and bronchial  tightness (5 hour delay).
       Heavier exposures have produced systemic effects with
       symptoms ranging from headache, nausea, and  lassitude to
       vomiting, chest or abdominal  pain, respiratory depression,
       extreme weakness, stupor,  convulsions and death (dependent
       upon concentration and time).]
9.1.5  Transfer crystals to another  clean beaker, add 200 mL of
       acetonitrile,  heat to boiling, and again let  crystals grow
       slowly at 40-60°C until 95% of the solvent has evaporated.
9.1.6  Repeat rinsing process as  described  in Section 9.1.4.
9.1.7  Take an aliquot of the second rinse, dilute  10 times with
       acetonitrile,  acidify with 1  ml of 3.8 M perchloric  acid
       per 100 mL of  DNPH solution,  and analyze by  HPLC.
9.1.8  The chromatogram illustrated  in Figure 4 represents  an
       acceptable impurity level  of  <0.025  ug/mL of formaldehyde
       in recrystallized DNPH reagent.  An  acceptable impurity
       level for an intended sampling application may be defined
       as the mass of the analyte (e.g. DNPH-formaldehyde deriva-
       tive) in a unit volume of  the reagent solution equivalent
       to less than one tenth (0.1)  the mass of the corresponding
       analyte from a volume of an air sample when the carbonyl
       (e.g. formaldehyde) is collected as  DNPH derivative  in  an
       equal unit volume of the reagent solution.  An impurity
       level unacceptable for a typical 10 L sample volume  may
       be acceptable if sample volume is increased to 100 L.
       The impurity level of DNPH should be below the sensitivity
       (ppb, v/v) level indicated in Table 1 for the anticipated
       sample volume.   If the impurity level is not acceptable
       for intended sampling application, repeat recrystallization.
       A  special glass  apparatus  should be used for the final  rinse
       and storage according to the following procedure:

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                        T011-10
        9.1.8.1  Transfer the crystals to the special glass appa-
                 ratus (Figure 3).
        9.1.8.2 -Add about 25 mL of acetonitrile, agitate gently,
                 and let solution equilibrate for 10 minutes.
        9.1.8.3  Drain the solution by properly positioning the
                 three-way stopcock.  [Note: The purified crystals
                 should not be allowed to contact laboratory air
                 except for a brief moment.  This is accomplished
                 by using the DNPH-coated silica cartridge on
                 the gas inlet of the special  glass apparatus.]
        9.1.8.4  After draining, turn stopcock so drain tube is
                 connected to measuring reservoir.
        9.1.8.5  Introduce acetonitrile through measuring reservoir.
        9.1.8.6  Rinsing should be repeated with 20-mL portions of
                 acetonitrile until  a satisfactorily low impurity
                 level  in the supernatant is confirmed by HPLC an-
                 alysis.  An impurity level  of <0.025 ug/mL formal-
                 dehyde should be achieved, as illustrated in
                 Figure 4.
 9.1.9  If special  glass apparatus is not available, transfer the
        purified crystals to an all-glass reagent bottle, add
        200 ml of acetonitrile, stopper,  shake gently, and let
        stand overnight.  Analyze supernatant  by HPLC according
        to Section  11.   The impurity level  should be comparable
        to that shown in Figure 4.
9.1.10  If the impurity level  is not satisfactory, pipet off the
        solution to waste, then add  25 mL of acetonitrile to the
        purified crystals.  Repeat Section 9.1.8.6.
9.1.11  If the impurity level  is satisfactory, add another 25 mL
        of acetonitrile, stopper and shake the reagent bottle,
        then set aside.  The saturated solution  above the purified
        crystals is the stock  DNPH reagent.
9.1.12  After purification,  purity of the DNPH reagent can be main-
        tained by storing in the special  glass apparatus.
9.1.13  Maintain only a minimum volume of saturated solution ade-
        quate for day to day operation.   This  will minimize wastage

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                            T011-11
            of purified reagent should it  ever become necessary  to  re-
            rinse the crystals to decrease the level  of impurity for
            applications requiring more stringent  purity specifications,
    9.1.14  Use clean pipets when removing saturated  DNPH stock
            solution for any analytical  applications.  Do not  pour  the
            stock solution from the reagent bottle.
9.2  Preparation of DNPH-Formaldehyde Derivative
     9.2.1  Titrate a saturated solution of DNPH in 2N HC1  with  formal-
            dehyde (other aldehydes or ketones may be used if  their de-
            tection is desirable).
     9.2.2  Filter the colored precipitate, wash with 2N HC1 and water
            and let precipitate air dry.
     9.2.3  Check the purity of the DNPH-formaldehyde derivative by
            melting point determination table or HPLC analysis.   If
            the impurity level  is not acceptable,  recrystallize  the
            derivative in ethanol.  Repeat purity  check and recrystal-
            lization as necessary until  acceptable level  of purity
            (e.g. 99%) is achieved.
9.3  Preparation of DNPH-Formaldehyde Standards
     9.3.1  Prepare a standard stock solution of the  DNPH-formal-
            dehyde derivative by dissolving accurately weighed
            amounts in acetonitrile.
     9.3.2  Prepare a working calibration  standard mix from the
            standard stock solution.  The  concentration of the
            DNPH-formaldehyde compound in  the standard mix solutions
            should be adjusted to reflect  relative distribution
            in a real  sample.  [Note:  Individual  stock solutions
            of approximately 100 mg/L are  prepared by dissolving
            10 mg of the solid derivative  in 100 ml of acetonitrile.
            The individual  solution is used to prepare calibra-
            tion standards containing the  derivative  of interest
            at concentrations of 0.5-20 ug/L, which spans  the
            concentration of interest for  most ambient air work.]
     9.3.3  Store all  standard solutions in a refrigerator. They
            should be stable for several months.

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                            T011-12
9.4  Preparation of DNPH-Coated Sep-PAK Cartridges
     [Note:   This procedure must be performed  in  an  atmosphere with  a
     very low aldehyde background.   All  glassware and  plastic  ware must
     be scrupulously cleaned and rinsed with deionized water and  alde-
     hyde free acetonitrile.  Contact  of reagents with laboratory air
     must be minimized.  Polyethylene  gloves must be worn  when handl-
     ing the cartridges.]
     9.4.1  DNPH Coating Solution
            9.4.1.1  Pipet  30 ml_ of saturated  DNPH stock solution to a
                     1000 ml volumetric flask  then add 500 mL  acetonitrile.
            9.4.1.2  Acidify with 1.0  ml of concentrated HC1.   [Note:
                     The atmosphere above the  acidified solution  should
                     preferably be  filtered through  a  DNPH-coated silica
                     gel  cartridge  to  minimize contamination from labora-
                     tory air.]  Shake solution then make  up to volume
                     with acetonitrile.   Stopper  the flask, invert and
                     shake  several  times until the solution is homogeneous.
                     Transfer the acidified solution to a  reagent bottle
                     with a 0-10 ml range positive displacement dispenser.
            9.4.1.3  Prime  the dispenser and slowly  dispense 10-20 ml
                     to waste.
            9.4.1.4  Dispense an aliquot solution to a sample  vial,
                     and  check the  impurity level  of the acidified
                     solution by HPLC  according to Section 9.1  and
                     illustrated in Figure 4.
            9.4.1.5  The impurity level  should be <0.025 ug/mL
                     formaldehyde similar to that  in the DNPH  coating
                     solution.
     9.4.2  Coating of Sep-PAK Cartridges
            9.4.2.1  Open the Sep-PAK  package, connect  the short  end
                     to a 10-mL syringe,  and place it  in the syringe
                     rack.   [Note:  Prepare as  many cartridges  and
                     syringes  as  possible.]
            9.4.2.2  Using  a positive  displacement repetitive  pipet,
                     add  10 ml of acetonitrile to  each  of  the  syringes.

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                 T011-13
 9.4.2.3   Let  liquid  drain to waste  by gravity.  [Note:
          Remove  any  air  bubbles that may be trapped between
          the  syringe and the silica cartridge by displacing
          them with the acetonitrile in the syringe.]
 9.4.2.4   Set  the repetitive dispenser containing the  acidi-
          fied DNPH coating solution to dispense 7 ml  into
          the  cartridges.
 9.4.2.5   Once the effluent flow at  the outlet of the  cart-
          ridge has stopped, dispense 7 ml of the coating
          reagent into each of  the syringes.
 9.4.2.6   Let  the coating re'agent drain by gravity through
          the  cartridge  until flow at the other end  of the
          cartridge stops.
 9.4.2.7   Wipe the excess liquid at  the outlet of each of
          the  cartridges  with clean  tissue paper.
 9.4.2.8   Assemble a  drying manifold with a  scrubber or
          "guard  cartridge" connected to each of the
          exit ports.  These  "guard  cartridges" are
          DNPH-coated and serve to remove any trace  of
          formaldehyde in the nitrogen gas supply.
 9.4.2.9   Remove  the  cartridges from the syringes and  con-
          nect the short  ends to the exit end of the scrub-
          ber  cartridge.
9.4.2.10   Pass nitrogen through each of the  cartridges at
          about 300-400 mL/min  for 5-10 minutes.
9.4.2.11   Within  10 minutes of  the drying process,  rinse
          the  exterior surfaces and  outlet ends of  the car-
          tridges with acetonitrile  using a  Pasteur  pipet.
9.4.2.12   Stop the flow of  nitrogen  after 15 minutes and
          insert  cartridge  connectors  (flared at both
          ends 0.25 OD x 1  in Teflon FEP tubing with ID
          slightly smaller  than the  OD  of the cartridge
          port) to the long  end of the  scrubber cartridges.
9.4.2.13  Connect the short  ends  of  a  batch  of the  coated
          cartridges  to the scrubbers  and pass  nitrogen
          at about 300-400  mL/min.
9.4.2.14  Follow procedure  in Section  9.4.2.11.

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                 T011-14
9.4.2.15  After 15 minutes,  stop  the  flow  of  nitrogen,
          remove the dried cartridges and  wipe the
          cartridge exterior free of  rinse acetonitrile.
9.4.2.16  Plug both ends of the coated cartridge with standard
          polypropylene  Luer® male plugs,  place the  plugged
          cartridge in a borosilicate glass culture  tube
          with polypropylene screw caps.
9.4.2.17  Put a serial number and a lot number label on
          each of the individual  cartridge glass storage
          container and  store the prepared lot in the
          refrigerator until  use.
9.4.2.18  Store cartridges in an  all-glass stoppered rea-
          gent bottle in a refrigerator until use.   [Note:
          Plugged cartridges could also be placed in screw-
          capped glass culture tubes  and placed in a refrig-
          erator until use.] Cartridges will  maintain their
          integrity for  up to 90  days stored  in refrigerated,
          capped culture tubes.
9.4.2.19  Before transport,  remove the glass-stoppered rea-
          gent bottles (or screw-capped glass culture tubes)
          containing the adsorbent tubes from the refriger-
          ator and place the tubes individually in labeled
          glass culture  tubes.  Place culture tubes  in a
          friction-top metal can  containing 1-2 inches of
          charcoal for shipment to sampling location.
9.4.2.20  As an alternative to friction-top cans for
          transporting sample cartridges,  the coated
          cartridges could be shipped in their individual
          glass containers.  A big batch of coated
          cartridges in individual glass containers  may
          be packed in a styrofoam box for shipment  to the
          field.  The box should  be padded with clean
          tissue paper or polyethylene-air bubble padding.
          Do not use polyurethane foam or  newspaper  as
          padding material.
9.4.2.21  The cartridges should  be immediately stored in a
          refrigerator upon arrival in the field.

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                            T011-15
10.   Sampling
     10.1   The sampling  system  is assembled  and  should  be similar
            to that shown in Figure  2.   [  Note: Figure 2(a)  illustrates
            a three tube/one pump configuration.   The tester should
            ensure that the  pump is  capable of  constant  flow rate
            throughout the sampling  period.]  The  coated  cartridges
            can be used as direct probes and  traps for sampling
            ambient air when the temperature  is above freezing.
            [Note: For sampling  ambient  air below freezing,  a short
            length (30-60 cm) of heated  (50-60°C)  stainless  steel tubing
            must be added to condition the air  sample prior  to
            collection on adsorbent  tubes.]   Two  types of sampling
            systems are shown in Figure  2. For purposes of  discussion,
            the following procedure  assumes the use of a dry test meter.
            [Note:  The dry  test meter may not  be accurate at flows
            below 500 mL/min and should  be backed up by  recorded
            flow readings at the start,  finish, and hourly intervals
            during sample collection.]
     10.2   Before sample collection, the  system  is checked  for leaks.
            Plug the input end of the cartridge so no flow is indicated
            at the output end of the pump. The mass flow meter should
            not indicate  any air flow through the sampling apparatus.
     10.3   The entire assembly  (including a  "dummy" sampling cartridge)
            is installed  and the flow rate checked at a  value near the
            desired rate.  In general, flow rates of 500-1200 mL/min
            should be employed.  The total moles  of carbonyl in the
            volume of air sampled should not  exceed that of  the DNPH
            concentration (  2 mg/cartridge).   In  general, a  safe
            estimate of the  sample size  should  be   75%  of the DNPH
            loading of the cartridge.  Generally,  calibration is
            accomplished  using a soap bubble  flow meter  or calibrated
            wet test meter connected to  the flow  exit, assuming the
            system is sealed. [Note: ASTM Method 3686 describes an
            appropriate calibration  scheme that does not require a
            sealed flow system downstream  of  the  pump.]

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                       T011/-16
10.4   Ideally,  a  dry  gas meter  is  included in the system to re-
       cord total  flow.   If  a dry gas meter is not available, the
       operator  must measure and record the sampling flow rate at
       the beginning and  end of  the sampling period to determine
       sample volume.   If the sampling period exceeds two hours,
       the flow  rate should  be measured at intermediate points
       during the  sampling period.   Ideally, a rotameter should
       be included to  allow  observation of the flow rate without
       interruption of the sampling process.
10.5   Before sampling, remove the  glass culture tube from the
       friction-top metal can or styrofoam box.  Let the cartridge
       warm to ambient temperature  in the glass tube before
       connecting  it to the  sample  train.
10.6   Using polyethylene gloves, remove the coated cartridge
       from the  glass  tube and connect it to the sampling system
       with a Luer® adapter  fitting.  Seal the glass tube for
       later use,  and  connect the cartridge to the sampling train
       so that its short  end becomes the sample inlet.  Record the
       following parameters  on the  sampling data sheet (Figure 5):
       date, sampling  location,  time, ambient temperature, baro-
       metric pressure (if available), relative humidity (if avail-
       able), dry  gas  meter  reading (if appropriate), flow rate,
       rotameter setting, cartridge batch number, and dry gas
       meter pump  identification numbers.
10.7   The sampler is  turned on  and the flow is adjusted to the
       desired rate.   A typical  flow rate through one cartridge is
       1.0 L/min and 0.8  L/min for  two tandem cartridges.
10.8   The sampler is  operated for  the desired period, with peri-
       odic recording  of  the variables listed above.
10.9   At the end  of the  sampling period, the parameters listed
       in Section  10.6 are recorded and the sample flow is stopped.
       If a dry  gas meter is not used, the flow rate must be checked
       at the end  of the  sampling interval.  If the flow rates at
       the beginning and  end of  the sampling period differ by more
       than 15%, the sample  should  be marked as suspect.

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                       T011-17
 10.10   Immediately after sampling, remove the cartridge (using
        polyethylene gloves) from the sampling system, cap with
        Luer* end plugs, and place it back In the original labeled
        glass culture tube.  Cap the culture tube, seal it with
        Teflon* tape, and place it in a friction-top can contain-
        ing  1-2 inches of granular charcoal or styrofoam box with
        appropriate padding.  Refrigerate the the culture tubes
        until analysis.  Refrigeration period prior to analysis
        should  not exceed 30 days.  [Note:  If samples are to be
        shipped to a central laboratory for analysis, the duration
        of the  non-refrigerated period should be kept to a
        minimum, preferably less than two days.]
10.11   If a dry gas meter or equivalent total flow indicator is
        not  used, the average sample flow rate must be calculated
        according to the following equation:
                       • Ql + Q? +  .  .  . QN
                  QA   •          	
                . . -   •      '     N'
        where:
                  QA    *   average  flow rate  (mL/min).
     Ql» Q2* • • • ON   *  fl°w rates determined at  beginning,  end,
                           and intermediate points during  sampling.
                    N   =  number of points averaged.
 10.12  The total flow rate is then calculated using the following
        equation:
                          (T2 - TX) x QA
                    V«n -  _
                              1000

        where:
                 Vm    -  total  volume (L) sampled at measured
                          temperature and pressure.
                 Tg    «  stop time (minutes).
                 TI    »  start time (minutes).
            ?2 - TI    •  total  sampling time (minutes).
                 QA    •»  average flow rate (mL/min).

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                                 T011-18
          10.13  The total volume (Vs) at standard conditions, 25°C and
                 760 mm Hg, is calculated from the following equation:

                             vs = Vm  x J>A x  298
                                        760    173" + fA
                 where:
                           Vs  =  total  sample volume (L)  at 25°C and
                                  760 mm Hg pressure.
                           Vm  =  total  sample volume (L)  at measured tem-
                           _      perature and pressure.
                           PA  =  average ambient  pressure (mm Hg).
                           t/\  =  average ambient  temperature (°C).
11.  Sample Analysis
     11.1  Sample Preparation
           11.1.1  The  samples are returned  to the laboratory in  a friction-
                   top  can containing 1-2 inches of granular charcoal and
                   stored  in  a refrigerator  until  analysis.   Alternatively,
                   the  samples may also  be stored  alone in their  individual
                   glass containers.   The time between  sampling and
                   analysis should  not exceed  30 days.
     11.2  Sample Desorption
           11.2.1  Remove  the  sample  cartridge  form the labeled culture tube.
                   Connect the sample  cartridge (outlet end  during sampling)
                   to a clean  syringe.   [Note:  The liquid flow during desorp-
                   tion should be  in the  reverse direction of air flow during
                   sample  collection.]
           11.2.2  Place the cartridge/syringe  in the syringe rack.
           11.2.3  Backflush the cartridge (gravity feed)  by passing 6 mL
                   of acetonitrile  from the syringe through  the cartridge
                   to a graduated test tube or to a 5-mL volumetric flask.
                   [Note:  A dry cartridge has an acetonitrile holdup volume
                   slightly greater than  1 ml.  The eluate flow may stop be-
                   fore the acetonitrile  in the syringe is completely drained
                   into the cartridge because of air trapped between the car-
                   tridge filter and the  syringe Luer® tip.  If this happens,
                   displace the trapped air with the acetronitrile in the
                   syringe using a long-tip disposable Pasteur pipet.]

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                            T011-19
      11.2.4  Dilute to  the  5-mL  mark with  acetonitrile.   Label the
              flask with sample identification.   Pipet two aliquots
              into sample vials with Teflon-lined  septa.   Analyze
              the first  aliquot for the  derivative carbonyls  by HPLC.
              Store the  second aliquot in the  refrigerator until
              sample analysis.
11.3  HPLC Analysis
      11.3.1  The HPLC system is  assembled  and calibrated  as  described
              in Section 11.4.  The operating  parameters are  as follows:

                     Column;     Zorbax  ODS (4.6  mm ID x 25 cm), or
                                 equivalent.
               Mobile Phase;     60% acetonitrile/40% water,  isocratic.
                   Detector;     ultraviolet,  operating at 360 nm.
                  Flow Rate;     1.0 mL/min.
             Retention Time:       7 minutes for  formaldehyde with
                                   one Zorbax  ODS column.
                                  13 minutes for  formaldehyde with
                                   two Zorbax  ODS columns.
    Sample Injection Volume;     25 uL.

              Before each analysis, the  detector  baseline  is  checked
              to ensure  stable conditions.
      11.3.2  The HPLC mobile phase is prepared by mixing  600 mL of
              acetonitrile and 400 mL of water.  This mixture is
              filtered through a  0.22-um polyester membrane filter
              in an all-glass and Teflon®  suction filtration  appa-
              ratus.  The filtered mobile  phase is degassed by pur-
              ging with  helium for 10-15 minutes  (100 mL/min) or
              by heating to 60°C  for  5-10  minutes in an Erlenmeyer
              flask covered with  a watch glass.  A constant back
              pressure restrictor (350 kPa) or short length (15-30 cm)
              of 0.25 mm (0.01 inch)  ID  Teflon® tubing should be
              placed after the detector  to  eliminate further  mobile
              phase outgassing.
      11.3.3  The mobile phase is placed in the HPLC solvent  reservoir
              and the pump is set at  a flow rate  of 1.0 mL/min and

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                       T011-20
         allowed  to  pump  for  20-30 minutes before the first analy-
         sis.   The detector is  switched on at least 30 minutes be^-
         fore  the first analysis, and the detector output is dis-
         played on a strip chart recorder or similar output device.
 11.3.4   A 100-uL aliquot of  the sample is drawn into a clean HPLC
         injection syringe.   The sample injection loop (25 uL) is
         loaded and  an  injection is made.  The data system, if
         available,  is  activated simultaneously with the injection,
         and the  point  of injection is marked on the strip chart
         recorder.
 11.3.5   After approximately  one minute, the injection valve is  '
         returned to the "inject" position and the syringe and
         valve are rinsed or  flushed with acetonitrile/water
         mixture  in preparation for the next sample analysis.
         [Note: The flush/rinse solvent should not pass  through
         the sample loop during flushing.] The loop is clean
         while the valve is in the "inject"  mode.
 11.3.6   After elution of the DNPH-formaldehyde  derivative
         (Figure 6),  data acquisition is terminated and  the
        component concentrations are calculated as described
         1n Section 12.
 11.3.7  After a stable baseline is achieved,  the system  can be
        used for  further  sample analyses  as  described above.
        [Note:  After several cartridge analyses,  buildup on
        the column may be removed  by flushing with  several
        column volumes of 100%  acetonitrile.]
11.3.8  If the concentration  of analyte exceeds  the linear  range
        of the instrument, the  sample should  be diluted with
        mobile phase,  or  a smaller  volume can be injected  into
        the HPLC.
11.3.9  If the retention  time is not  duplicated  (+10%), as  de-
        termined  by  the calibration  curve, the  acetonitrile/water
        ratio  may be increased  or  decreased to  obtain the correct
        elution time.   If the elution time  is too  long, increase

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                           T011-21
             the  ratio;  if it is too short, decrease the ratio.
              [Note:  The  chromatographic conditions described here
              have been optimized for the detection of formaldehyde.
              Analysts are advised to experiment with their HPLC
              system  to optimize chromatographic conditions for
              their particular analytical needs.]
11.4  HPLC Calibration
      11.4.1  Calibration standards  are prepared in acetonitrile
              from the DNPH-formaldehyde derivative.   Individual
              stock solutions of  100 mg/L are  prepared by dissolving
              10 mg of solid  derivative in  100 ml  of mobile phase.
              These individual solutions are used  to prepare calibration
              standards  at concentrations spanning the range of interest.
      11.4.2  Each calibration standard  (at least  five levels) is
              analyzed three  times  and  area response is  tabulated
              against mass injected  (Figure 7). All calibration
              runs are  performed  as  described  for  sample analyses
              in Section  11.3.   Using the UV detector, a linear
              response  range  of  approximately  0.05-20  ug/L  should  be
              achieved  for 25-uL  injection  volumes.  The results may
              be used to prepare  a  calibration curve,  as illustrated
              in Figure  8.  Linear  response is indicated where a
              correlation coefficient  of  at least  0.999  for a  linear
              least-squares fit  of  the  data (concentration  versus
              area response)  is  obtained.   The retention times for
              each analyte should agree within 2%.
      11.4.3  Once linear response  has  been documented,  an  intermediate
              concentration standard near the  anticipated levels  of
              each component, but at least  10  times  the  detection
              limit, should be chosen for daily calibration.   The  day
              to day response for the various  components should  be
              within 10% for analyte concentrations  1  ug/mL or greater
              and within 15-20% for analyte concentrations  near  0.5 ug/mL.
              If  greater variability is observed,  recalibration  may be
              required or a new calibration curve must be developed
              from fresh standards.

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                                 T011-22
           11.4.4  The response for each component in the daily calibra-
                   tion standard is used to calculate a response factor
                   according to the following equation:
                   where:
                            RFC =  response factor (usually area counts)
                                   for the component  of interest in nano-
                                   grams injected/response  unit.
                            Cc  = concentration  (mg/L)  of analyte in  the
                                   daily calibration  standard.
                            Vj  =  volume (uL) of calibration  standard  injected
                             Rc =  response (area counts) for  analyte in
                                   the calibration standard.
12.   Calculations
     12.1  The  total  mass of analyte  (DNPH-formaldehyde)  is calculated
           for  each  sample using  the  following equation:
                      Wd   =  RFC  x  Rd  x VE/VI
           where:
                      Wd   =  total  quantity of analyte  (ug) in the  sample.
                     RFC   =  response  factor calculated in Section  11.4.4.
                      Rd   =  response  (area counts or other response  units)
                             for  analyte  in sample extract, blank corrected.
                          =  [(As)  (VD/VA)  - (Ab)(vb/vs)]
                             where:
                               As   =   area counts, sample.
                               Ab   =   area counts, blank.
                               Vb   =   volume (ml), blank.'
                               Vs   =   volume (ml), sample.
                      VE   =  final  volume  (mL) of sample extract.
                      Vj   =  volume of extract (uL) injected into the HPLC
                             system.
                      VD   =   redilution volume (if sample was rediluted).
                      VA   =   aliquot used for redilution  (if sample was
                             rediluted).

-------
                                T011-23
     12.2   The  concentration of formaldehyde in the original sample is cal-
           culated  from the following equation:
                                 Wd
                       C  =          .     x 1000
                                     Vs)
           where:
                       CA   =   concentration of analyte  (ng/L) in the orig-
                              inal sample.
                       Wd   =   total quantity of analyte  (ug) in sample, blank
                              corrected.
                       Vm   =   total sample volume  (L) under ambient conditions
                       Vs   =   total sample volume  (L) at 25°C and  760 mm Hg.
           The  analyte  concentrations can be converted to ppbv using the
           following  equation:
                 CA (ppbv)  =  CA  (ng/L) x 24.4
                                        MWA
           where:
                     CA(ppbv) =  Concentration of analyte in parts  per
                                billion by volume.
                     CA (ng/L)  is calculated using  Vs.
                           =   .molecular weight of  analyte.
13.   Performance Criteria and  Quality  Assurance
     This section summarizes  required  quality  assurance measures  and
     provides guidance concerning performance  criteria that  should  be
     achieved within each laboratory.
     13.1  Standard Operating  Procedures  (SOPs).
           13.1.1  Users should generate  SOPs  describing  the following
                   activities  in their laboratory:   (1) assembly, cali-
                   bration, and operation of the  sampling system, with
                   make and model of equipment used;  (2)  preparation,

-------
                             T011-24
               purification,  storage,  and  handling  of  sampling  reagent
               and samples;  (3)  assembly,  calibration,  and  operation
               of the  HPLC system,  with make  and model  of equipment
               used; and  (4)  all  aspects of data recording  and  processing,
               including  lists of computer hardware and software used.
       13.1.2   SOPs should provide  specific stepwise instructions and
               should  be  readily  available to and understood by the
               laboratory personnel  conducting the work.
 13.2   HPLC System Performance
       13.2.1   The general appearance of the HPLC system should be
               similar to that illustrated in Figure 1.
       13.2.2   HPLC system efficiency is calculated according to the
               following equation:
                     N
              where:
                   N      column efficiency (theoretical  plates).
                   tr  =  retention time (seconds) of analyte.
                 Wi/g  =  width of component peak at half height
                          (seconds).
              A column efficiency of >5,000 theoretical  plates should
              be obtained.
      13.2.3  Precision of response for replicate HPLC injections should
              be +10% or less,  day to day,  for analyte calibration
              standards at 1 ug/mL or greater  levels.   At 0.5 ug/mL  level
              and below, precision of replicate analyses  could vary  up
              to 25%.  Precision of retention  times  should be ^2% on
              a given day.
13.3  Process Blanks
      13.3.1  At least one field blank  or 10%  of the field samples,
              whichever is larger, should be shipped and  analyzed with
              each group of samples.  The number of  samples within a

-------
                                T011-25
                  group and/or time  frame  should  be  recorded so that a
                  specified percentage  of  blanks  is  obtained for  a given
                  number of field samples.  The  field  blank is treated
                  identically to the samples except  that  no air is drawn
                  through the cartridge.   The performance criteria de-
                  scribed in Section 9.1  should  be met for process blanks.
    13.4  Method Precision and Accuracy
          13.4.1  At least one duplicate sample  or 10% of the  field  sam-
                  ples, whichever is larger, should  be collected  during
                  each sampling episode.  Precision for field  replication
                  should be _+20% or better.
          13.4.2  Precision for replicate HPLC injections should be +10%
                  or better,  day to day,  for calibration standards.
          13.4.3  At least one  sample spike with analyte of interest or
                  10%  of the  field  samples, whichever is larger, should
                  be collected.
          13.4.4  Before initial use of the method, each laboratory should
                  generate triplicate spiked samples at  a minimum of three
                  concentration levels, bracketing  the range of  interest
                  for  each compound.  Triplicate nonspiked samples must
                  also be  processed.  Spike  recoveries of >80 _+  10% and
                  blank levels  as outlined  in Section 9.1 should be
                  achieved.

14.  Detection  of  other Aldehydes  and Ketones
     [Note:   The procedure outlined  above  has  been written specifically
     for the sampling  and analysis  of  formaldehyde in  ambient air using
     an adsorbent  cartridge and HPLC.   Ambient air contains other alde-
     hydes and ketones.  Optimizing  chromatographic  conditions by using two
     Zorbax  ODS columns in series and  varying  the mobile  phase composition
     through a gradient program will enable the  analysis  of other aldehydes
     and ketones.]

-------
                            T011-26
14.1  Sampling Procedures
      Same as Section 10.
14.2  HPLC Analysis
      14.2.1  The HPLC system is  assembled  and  calibrated as described
             in  Section  11.   The operating parameters are as follows:
                     Column;   Zorbax ODS,  two  columns in series
              Mobile Phase:   Acetonitrile/water, linear gradient
                     Step 1.   60-75% acetonitrile/40-25% water in 30
                             minutes.
                     Step 2.   75-100% acetonitrile/25-0% water in
                             20 minutes.
                     Step 3.  100% acetonitrile for 5 minutes.
                    Step 4.  60% acetonitrile/40% water reverse gra-
                             dient in 1 minute.
                    Step 5.  60% acetonitrile/40% water,  isocratic, for
                             15 minutes.
                  Detector;  Ultraviolet,  operating at  360  nm
                 Flow Rate;  1.0 mL/min
   Sample Injection  Volume:   25 uL

     14.2.2  The gradient program allows for optimization of chromato-
             graphic conditions  to separate acrolein, acetone,
             propionaldehyde,  and other higher molecular weight  alde-
             hydes and ketones  in an analysis  time  of about one
             hour.   Table 1  illustrates  the sensitivity for selective
             aldehydes and  ketones that  have been identified using
             two Zorbax  ODS  columns in  series.
     14.2.3   The chromatographic  conditions described here have  been
             optimized for a gradient HPLC  (Varian Model 5000) sys-
             tem equipped with a  UV detector (ISCO Model 1840 variable
             wavelength), an automatic sampler with a 25-uL loop
             injector  and two DuPont Zorbax ODS columns (4.6 x 250
             mm), a recorder, and an electronic integrator.   Analysts
             are  advised to experiment with their HPLC systems  to
             optimize chromatographic conditions for their particular
             analytical needs.  Highest chromatographic resolution
            and sensitivity are desirable  but  may not be  achieved.

-------
                      T011-27
        The  separation of  acrolein, acetone, and propionaldehyde
        should be a minimum  goal  of the optimization.
14.2.4  The  carbonyl  compounds  in the  sample are identified and
        quantified by comparing their  retention times and  area
        counts with those  of standard  DNPH  derivatives.  Formal-
        dehyde, acetaldehyde, acetone, propionaldehyde, croton-
        aldehyde, benzaldehyde, and o-, m-, p-tolualdehydes can
        be identified with a high degree  of confidence.  The
        identification of  butyraldehyde is  less certain because
        it coelutes with isobutyraldehyde and  methyl ethyl
        ketone under the stated chromatographic conditions.
        Figure 10 illustrates a typical chromatogram obtained
        with the gradient  HPLC system.
14.2.5  The concentrations of individual  carbonyl  compounds are
        determined as outlined in Section 12.
14.2.6  Performance criteria and  quality  assurance activities
        should meet those requirements outlined  in Section 13.

-------
                                   T011-28

                                  REFERENCES
      S  yestre B. Tejada, "Standard Operating Procedure For DNPH-coated
      Silica Cartridges For Sampling Carbonyl Compounds In Air And Analysis
      by High-performance Liquid Chromatography," Unpublished, U.S.
      Environmental Protection Agency, Research Triangle Park, NC, March
      19oo.

  2.  Silvestre B. Tejada, "Evaluation of Silica Gel  Cartridges Coated  in
      |itu with Acidified 2,4-Dinitrophenylhydrazine  for Sampling Aldehydes
      and Ketones in Air", Intern.  J.  Environ.  Anal.  Chem..  26:167-185,  1986.

  3.  Quality Assurance Handbook for Air Pollution  Measurement Systems,
      Volume ii - Ampient Air  Specific Methods.  LPA-bOQ/4-77-n?7AT  n. s
      Environmental  Protection Agency, Research  Triangle Park, NC,  July
      A .7 / y •

  4.  J. 0. Levin,  et  al., "Determination  of  Sub-part-per-Million  Levels
      of Formaldehyde  in  Air Using  Active  or  Passive  Sampling  on  2,4-
      Dinitrophenylhydrazine-Coated  Glass  Fiber  Filters  and High-Performance
      Liquid Chromatography",  Anal.  Chem.. J57:1032-1035,  1985.

  5*  Compendium  of Methods for the  Determination of  Toxic Organic Compounds
      in Ambient  Air.  hPA-60Q/4-84-Q4i.  n.s.  Fnw^nn^n^i pr»tfct1on  	
      Agency, Research  Triangle  Park,  NC, April  1984.

  6.  J. E.  Sigsby, Jr., et al., unpublished  report on volatile organic
      compound  emissions  from  46 in-use  passenger cars, U.S. Environmental
      Protection Agency, Research Triangle Park, NC,  1984.

  7.   S. B.  Tejada and W.  D. Ray, unpublished results of study of aldehyde
      concentration in indoor atmosphere of some residential  homes, U.S.
      Environmental Protection Agency,  Research Triangle Park, NC, 1982.

  8.   J. M.  Perez, F. Lipari, and D. E. Seizinger, "Cooperative Development
      of Analytical Methods for Diesel  Emissions and Particulates - Solvent
      Extractions, Aldehydes and Sulfate Methods", presented  at the Society
      of Automotive Engineers International Congress and Exposition, Detroit,
     MI, February-March 1984.

 9.  R.  M. Riggin, Technical  Assistance Document for  Sampling and Analysis
     of Toxic Organic Compounds in  Ambient Air.  EPA-600/4-83-Q27. U s  	
     Environmental  Protection  Agency,  Research  Triangle Park,  NC, June
     1983.

10.  E.  V. Kring, et  al., "Sampling for Formaldehyde  in  Workplace and
     Ambient Air  Environments  - Additional  Laboratory Validation  and Field
     Verification of  a Passive Air  Monitoring Device  Compared  with  Conventional
     Sampling Methods", J. Am. Ind.  Hyg. Assoc..  45:318-324,  1984.

-------
                                  T011-29
11.  I. Ahonen,  E.  Priha, and M-L Aijala,  "Specificity  of Analytical  Methods
     Used to Determine the Concentration of  Formaldehyde  in  Workroom
     Air", Chemosphere, 1_3:521-525,  1984.
12.  J.J. Bufalini  and K.L.  Brulkker, "The Photooxidation of Formaldehyde
     at Low Pressures." In:   Chemical Reaction in  Urban Atmospheres,
     (ed. C.S. Tuesday), (American Elsevier  Publishing  Co.,  New York,
     1971), pp.  225-240.
13.  A.P. Altshuller and I.R. Cohen, Science 7, 1043 (1963).
14.  Committee on Aldehydes, Board of Toxicology and Environmental  Hazards,
                            •-  "Formaldehyde and  Other Aldehydes"  (National
National Research Council,
Academy Press, Washington,
                                DC, 1981).

-------
Sample Volume, L
                               TABLE 1.  SENSITIVITY (PPB.V/V)  OF SAMPLING/ANALYSIS  FOR

                         ™.T    ALDEHYDES AND KETONES IN AMBIENT AIR USING ADSORBENT
                         CARTRIDGE FOLLOWED BY GRADIENT HIGH PERFORMANCE  LIQUID  CHROMATOGRAPHY
10
20
30
40
                                                       50
                                   60
                                  100     200     300     400     500   1000
Compound
Formaldehyde
Acet aldehyde
Acroleln
Acetone
Propionaldehyde
Crotonaldehyde
Butyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
o-tolualdehyde
m-tolualdehyde
p-tolualdehyde
Hexanaldehyde
2,5-Dimethylbenzaldehyde
1.45
1.36
1.29
1.28
1.28
1.22
1.21
1.07
1.15
1.15
1.02
1.02
1.02
1.09
0.97
Sensiti
0.73
0.68
0.65
0.64
0.64
0.61
0.61
0.53
0.57
0.57
0.51
0.51
0.51
0.55
0.49
vity (ppb
0.48
0.45
0.43
0.43
0.43
0.41
0.40
0.36
0.38
0.38
0.34
0.34
0.34
0.36
0.32
, v/v)
0.36
0.34
0.32
0.32
0.32
0.31
0.30
0.27
0.29
0.29
0.25
0.25
0.25
0.27
0.24
of DNPH/HPLC
0.29 0.24
0.27 0.23
0.26 0.22
0.26 0.21
0.26 0.21
0.24 0.20
0.24 0.20
0.21 0.18
0.23 0.19
0.23 0.19
0.20 0.17
0.20 0.17
0.20 0.17
0.22 0.18
0.19 0.16
Method
0.15
0.14
0.13
0.13
0.13
0.12
0.12
0.11
0.11
0.11
0.10
0.10
0.10
0.11
0.10
Carbonyls
0.07 0.05
0.07 0.05
0.06 0.04
0.06 0.04
0.06 0.04
0.06 0.04
0.06 0.04
0.05 0.04
0.06 0.04
0.06 0.04
0.05 0.03
0.05 0.03
0.05 0.03
0.05 0.04
0.05 0.03
in Ambient Air
0.04 0.03 0.01
0.03 0.03 0.01
0.03 0.03 0.01
0.03 0.03 0.01
0.03 0.03 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.03 0.02 0.01
0.02 0.02 0.01
 [Note:  PPb values are measured at 1 atm and 25'C;  sample  cartridge  is  eluted  with  5 mL
         acetomtnle, and 25 mL are injected onto  HPLC  column.]


 [Note:  Maximum sampling flow through a DNPH-coated  SEP-PAK  is about  1.5 L  per minute.]
                                                                                                               I
                                                                                                              CO
                                                                                                              o

-------
                     INJECTION
                       VALVE
                                    COLUMN
tr
                                         VARIABLE
                                       WAVELENGTH
                                           UV
                                         DETECTOR
 MOBILE
 PHASE
RESERVOIR
                             DATA
                            SYSTEM
                          STRIP CHART
                           RECORDER
                                                                             CO
                   FIGURE 1. TYPICAL HPLC SYSTEM

-------
       OIL-LESS
         PUMP
       VENT
                                TOll-32
                      MASS FLOW
                      CONTROLLERS
                                        Couplings to
                                        connect
                                        DNPH-coated Sep-PAK
                                        Adsorbent Cartridges
                       (a) MASS FLOW CONTROL
                    ROTAMETER
VENT
• 	 . n
DRY
TEST
METER



=
i
•••




PUMP

••M
N
\
T
-*r=l
EEDLE
fALVE
  (DRY TEST METER SHOULD NOT BE USED
  FOR FLOW OF LESS THAN 500 ml/minute)
Coupling to
connect
DNPH-coated
Sep-PAK
Adsorbent
Cartridges
                    (b) NEEDLE VALVE/DRY TEST METER
    FIGURE 2. TYPICAL SAMPLING SYSTEM CONFIGURATIONS

-------
                        T011-33
                                    DNPH-COATED Si02
       DNPH
     CRYSTALS
     HIGH-POROSITY
        FRIT
                           THREE-WAY STOPCOCK
FIGURE 3.
SPECIAL GLASS APPARATUS FOR RINSING,
STORING, AND DISPENSING SATURATED
DNPH STOCK SOLUTION

-------
          DNPH Reagent
Solvent Front
                                                                      OJ
                                                                      -p.
                   10
20
                                       30
40
                                TIME, min
                 FIGURE 4. IMPURITY LEVEL OF DNPH
                          AFTER RECRYSTALLIZATION
50

-------
                                  T011-35
PROJECT:


SITE:
                       SAMPLING  DATA SHEET
                    (One Sample per  Data Sheet)



                                   DATE(S) SAMPLED:
LOCATION:
                                   TIME PERIOD SAMPLED:_


                                   OPERATOR:
INSTRUMENT MODEL NO:.


PUMP SERIAL NO:
                                   CALIBRATED BY:
ADSORBENT  CARTRIDGE INFORMATION:
        Type:	
   Adsorbent:_	


SAMPLING DATA:


        Start Time:
                            Serial  Number:_
                            Sample  Number:"
                                  Stop  Time:
Time





Avg.
Dry Gas
Meter
Reading






Rotameter
Reading


*



Flow
Rate (Q)*f
mL/min






Ambient
Temperature,
°C






Barometric
Pressure,
mm Hg






Relative
Humidity, %






Comments






*  Flow rate from  rotameter or soap  bubble calibrator (specify which)


Total Volume Data  (Vm) (use data from dry gas meter, if available)


     Vm =  (Final  - Initial) Dry Gas Meter Reading, or                =	Liters
"m

or
           Qi + Qz  + Qs - • • QN
     V  =                       x                 1
           	R1000 x  (Sampling Time in  Minutes)
'm
                                                                       Liters
     FIGURE 5.
                   EXAMPLE SAMPLING  DATA SHEET

-------
                                T011-36
      OPERATING PARAMETERS
              HPLC
Column: Zorbax ODS or C-18 RP
Mobile Phase: 60% Acetonitrile/40% Water
Detector: Ultraviolet, operating at 360 nm
Flow Rate: 1 mL/min.
Retention Time: -  7 minutes for formaldehyde
Sample Injection Volume: 25 uL
                                z
                                c_
                                m
1
0

1 1 1
10
TIME, min
|
20

FIGURE 6.
CHROMATOGRAM OF DNPH-FORMALDEHYDE
DERIVATIVE

-------
                                 T011-37
      OPERATING PARAMETERS
              HPLC
 Column: Zorbax ODS or C-18 RP
 Mobile Phase: 60°/o Acetonitrile/40% Water
 Detector: Ulltraviolet, operating at 360 nm
 Flow Rate: 1 mL/min.
.Retention Time: ~  7 minutes for formaldehyde
 Sample Injection Volume: 25 uL            (a)
       T

       2  61 ug/mL
       -3
                                        T
                                        6
      TIME-*
   m  1.23ug/mL
   z
                                                           6.16ug/mL
           CONC
          .61 ug/mL
         1.23 ug/mL
         6.16ug/mL
        12.32ug/mL
        18.48ug/ml_
 AREA
COUNTS
  226541
  452166
 2257271
 4711408
 6953812
                                       (d)
                                        (e)

                                T
                               ts
                               LU
                               "3
            T
TIME ->      ^
12.32ug/mL  yj
            z
                                   TIME-*
                                   18.48ug/mL
    FIGURE 7.
 HPLC CHROMATOGRAM  OF VARYING CON
 CENTRATIONS OF DNPH-FORMALDEHYDE
 DERIVATIVE

-------
                             T011-38
   o
   o
   <
   LU
   OC
CORRELATION COEFFICIENT:
          0.9999
                                       OPERATING PARAMETERS
                                               HPLC
                                 Column: Zorbax ODS or C-18 RP
                                 Mobile Phase: 60% Acetonitrile/40% Water
                                 Detector: Ultraviolet, operating at 360 nm
                                 Flow Rate: 1 mL/min
                                 Retention Time: ~ 7 minutes for formaldehyde
                                 Sample Injection Volume: 25 uL
                  3       6      9      12      15      18

                  DNPH-Formaldehyde Derivative (ug/mL)
FIGURE 8.      CALIBRATION CURVE FOR FORMALDEHYDE

-------
                                                               Revision 1.0
                                                               June, 1987
                               METHOD T012
   METHOD FOR THE DETERMINATION OF  NON-METHANE  ORGANIC  COMPOUNDS  (NMOC)
     IN AMBIENT AIR USING CRYOGENIC PRECONCENTRATION  AND DIRECT FLAME
                       IONIZATION DETECTION  (PDFID)
1.   Scope

     1.1  In recent years,  the relationship between  ambient  concentrations
          of precursor organic compounds  and subsequent  downwind  concentra-
          tions of ozone has been described by a  variety of  photochemical
          dispersion models.  The most important  application of such models
          is to determine the degree of control  of precursor organic com-
          pounds that is necessary in an urban area  to achieve compliance
          with applicable ambient air quality standards  for  ozone (1,2).
     1.2  The more elaborate theoretical  models generally require detailed
          organic species data obtained by multicomponent gas chromatography (3)
          The Empirical Kinetic Modeling Approach (EKMA), however, requires
          only the total non-methane organic compound (NMOC) concentration
          data; specifically, the average total NMOC concentration from 6
          a.m. to 9 a.m. daily at the sampling location.  The use of total
          NMOC concentration data in the EKMA substantially reduces the
          cost and complexity of the sampling and analysis system by not
          requiring qualitative and quantitative species identification.
     1.3  Method T01,  "Method for The Determination of Volatile Organic
          Compounds in  Ambient Air Using Tenax® Adsorption and Gas
          Chromatography/Mass Spectrometry  (GC/MS)", employs collection
          of certain  volatile organic compounds on Tenax® GC with subse-
          quent analysis by thermal desorption/cryogenic preconcentration
          and GC/MS  identification.  This method  (T012) combines the same
          type of cryogenic concentration technique used in Method T01
          for  high  sensitivity with the  simple flame  ionization detector
          (FID) of the GC  for total NMOC measurements, without the GC
          columns  and complex procedures necessary  for  species separation.

-------
                                  T012-2
     1.4  In a flame ionization detector, the sample is injected into a
          hydrogen-rich flame where the organic vapors burn producing
          ionized molecular fragments.  The resulting ion fragments are
          then collected and detected.  The FID is nearly a universal
          detector.  However, the detector response varies with the species
          of [functional group in] the organic compound in an  oxygen atmos-
          phere.  Because this method employs a helium or argon carrier
          gas, the detector response is nearly one for all  compounds.
          Thus, the historical short-coming of the FID involving varying
          detector response to different organic functional  groups  is
          minimized.
     1.5  The method can be used either for direct, in situ ambient
          measurements or (more commonly) for analysis of integrated
          samples collected in specially treated stainless steel  canisters.
          EKMA models generally require 3-hour integrated NMOC measurements
          over the 6 a.m. to 9 a.m. period and are used by State or local
          agencies to prepare State Implementation Plans (SIPs)  for ozone
          control to achieve compliance with the National  Ambient Air
          Quality Standards (NAAQS) for ozone.  For direct,  in situ ambient
          measurements, the analyst must be present during  the 6 a.m.  to
          9 a.m. period, and repeat measurements (approximately  six per
          hour) must be taken to obtain the 6 a.m. to 9 a.m. average
          NMOC concentration.  The use of sample canisters  allows the
          collection of integrated air samples over the 6 a.m. to 9 a.m.
          period by unattended, automated samplers.  This method has
          incorporated both sampling approaches.
2.  Applicable Documents
    2.1   ASTM Standards
          D1356 - Definition of Terms Related to Atmospheric
                  Sampling and Analysis
           E260 - Recommended Practice for General  Gas Chromato-
                  graphy Procedures
           E355 - Practice for Gas Chromatography Terms and
                  Relationships

-------
                                  T012-3
     2.2  Other Documents
            U.  S.  Environmental  Protection Agency Technical Assistance
            Documents  (4,5)
            Laboratory and  Ambient Air  Studies  (6-10)
3.  Summary of  Method
     3.1   A whole air sample  is either extracted directly from the ambient
           air  and analyzed  on site by  the GC system or collected into a
           precleaned  sample canister and analyzed off site.
     3.2   The  analysis requires drawing a fixed-volume portion of the
           sample  air  at a  low flow rate through a glass-bead filled trap
           that is cooled to approximately -186°C with liquid argon.  The
           cryogenic trap  simultaneously collects and concentrates the
           NMOC (either via  condensation or  adsorption) while allowing
           the  methane, nitrogen,  oxygen, etc.  to pass through the trap
           without retention.   The system is dynamically calibrated so
           that the volume  of  sample passing through the trap does not
           have to be  quantitatively measured,  but must be precisely
           repeatable  between  the  calibration and the analytical phases.
     3.3   After the fixed-volume  air sample has been drawn through the
           trap, a helium carrier  gas flow is diverted to pass through
           the  trap, in the  opposite direction  to the sample flow, and
           into an FID.  When  the  residual air  and methane have been
           flushed from the  trap and the FID baseline restabilizes,
           the  cryogen is  removed  and the temperature of the trap is
           raised  to approximately 90°C.
     3.4   The  organic compounds previously  collected in the trap revol-
           atilize due to the  increase  in temperature and are carried into
           the  FID, resulting  in a response  peak or peaks from the FID.
           The  area of the  peak  or peaks is  integrated, and the integrated
           value is translated to  concentration units via a previously-
           obtained calibration  curve relating  integrated peak areas with
           known concentrations  of propane.
     3.5   By convention, concentrations of  NMOC are reported in units of
           parts per million carbon (ppmC),  which, for a specific compound,
           is the  concentration  by volume (ppmV) multiplied by the number
           of carbon atoms  in  the  compound.

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                             T012-4
3.6   The cryogenic trap simultaneously concentrates  the NMOC while
      separating and removing the methane from air samples.   The
      technique is thus direct reading  for NMOC and,  because  of
      the concentration step, is more sensitive than  conventional
      continuous NMOC analyzers.
Significance
4.1   Accurate measurements of ambient  concentrations of NMOC
      are important for the control  of  photochemical  smog because
      these organic compounds are primary precursors  of  atmospheric
      ozone and other oxidants.  Achieving and maintaining compliance
      with the NAAQS for ozone thus depends largely on control of
      ambient levels of NMOC.
4.2   The NMOC concentrations typically found at urban sites  may
      range up to 5-7 ppmC or higher.  In order to determine  transport
      of precursors into an area, measurement of NMOC upwind  of the
      area may be necessary.  Upwind NMOC concentrations are  likely
      to be less than a few tenths of 1 ppm.
4.3   Conventional methods that depend  on gas chromatography  and
      qualitative and quantitative species evaluation are excessively
      difficult and expensive to operate and maintain when speciated
      measurements are not needed.  The method described here involves
      a simple, cryogenic preconcentration procedure  with subsequent,
      direct, flame ionization detection.  The method is sensitive and
      provides accurate measurements of ambient NMOC  concentrations
      where speciated data are not required as applicable to  the
      EKMA.
Definitions
[Note:  Definitions used in this document and in any  user-prepared
Standard Operating Procedures (SOPs) should be consistent with ASTM
Methods D1356 and E355.  All abbreviations and symbols are defined
within this document at point of use.]

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                            T012-5
5.1   Absolute pressure - Pressure measured  with  reference  to  absolute
      zero pressure (as opposed to atmospheric  pressure), usually  ex-
      Pressed as pounds-force per square  inch  absolute  (psia).
5.2   Cryogen - A substance used to obtain  very low trap temperatures
      in the NMOC analysis system.  Typical  cryogens are liquid  argon
      (bp -185.7) and liquid oxygen (bp-183.0).
5.3   Dynamic calibration - Calibration of  an  analytical system  with
      pollutant concentrations that are generated in a  dynamic,  flow-
      ing system, such as by quantitative,  flow-rate dilution  of a
      high concentration gas standard with  zero gas.
5.4   EKMA - Empirical Kinetics Modeling  Approach; an empirical  model
      that attempts to relate morning ambient  concentrations of  non-
      methane organic compounds (NMOC) and  NOX  with subsequent peak,
      downwind ambient ozone concentrations; used by pollution control
      agencies to estimate the degree of  hydrocarbon emission  reduction
      needed to achieve compliance with national  ambient air quality
      standards for ozone.
5.5   Gauge pressure - Pressure measured  with  reference to  atmospheric
      pressure (as opposed to absolute pressure).  Zero gauge  pressure
      (0 psig) is equal to atmospheric pressure,  or 14.7 psia  (101 kPa).
5.6   in situ - In place; in situ  measurements are obtained by  direct,
      on-the-spot analysis, as opposed to subsequent, remote analysis
      of a collected sample.
5.7   Integrated sample - A sample obtained  uniformly over  a specified
      time period and representative of the  average levels  of  pollutants
      during the time period.
5.8   NMOC - Nonmethane organic compounds;  total  organic compounds as
      measured by a flame ionization detector,  excluding methane.
5.9   ppmC - Concentration unit of parts  per million carbon; for a spe-
      cific compound, ppmC is equivalent  to  parts per million  by volume
      (ppmv) multiplied by the number of  carbon atoms in the compound.
5.10  Sampling - The process of withdrawing  or  isolating a  representative
      portion of an ambient atmosphere, with or without the simultaneous
      isolation of selected components for  subsequent analysis.

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                                  T012-6
6.  Interferences
     6.1   In field and laboratory evaluation,  water  was  found  to  cause  a
           positive shift in the  FID baseline.   The effect  of this shift
           is minimized by carefully selecting  the integration  termination
           point and adjusted baseline  used  for calculating the area  of
           the NMOC peak(s).
     6.2   When using helium as a carrier  gas,  FID response is  quite
           uniform for most hydrocarbon  compounds, but the  response can
           vary considerably for  other  types  of organic compounds.
7.   Apparatus
     7.1   Direct Air Sampling  (Figure  1)
           7.1.1   Sample manifold or sample  inlet line - to bring
                   sample air into the  analytical system.
           7.1.2   Vacuum pump or blower - to draw sample air through a
                   sample manifold or long inlet  line to  reduce inlet
                   residence time.  Maximum  residence time  should  be  no
                   greater than 1 minute.
     7.2   Remote Sample  Collection  in  Pressurized Canisters (Figure  2)
           7.2.1   Sample canister(s) -  stainless steel, Summa®-polished
                   vessel(s)  of 4-6  L capacity  (Scientific  Instrumentation
                   Specialists, Inc., P.O. Box  8941, Moscow, ID 83843), used
                   for automatic  collection of  3-hour integrated field
                   air samples.   Each canister  should have  a unique identi-
                   fication number stamped on its frame.
           7.2.2   Sample pump -  stainless steel, metal bellows  type
                   (Model  MB-151,  Metal  Bellows Corp., 1075 Providence
                   Highway, Sharon,  MA  02067) capable of 2  atmospheres
                   minimum output  pressure.   Pump must be free  of  leaks,
                   clean, and uncontaminated  by oil or organic  compounds.
           7.2.3   Pressure gauge  -  0-30 psig (0-240 kPa).
           7.2.4   Solenoid valve  -  special electrically-operated, bistable
                   solenoid valve  (Skinner Magnelatch Valve, New Britain}

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                            T012-7
             CT), to control sample flow to the canister with negligi-
             ble temperature rise (Figure 3).  The use of the Skinner
             Magnelatch valve avoids any substantial  temperature rise
             that would occur with a conventional, normally closed
             solenoid valve, which would have to be energized during
             the entire sample period.  This temperature rise in the
             valve could cause outgasing of organics  from the Viton
             valve seat material.  The Skinner Magnelatch valve
             requires only a brief electrical pulse to open or close
             at the appropriate start and stop times  and therefore
             experiences no temperature increase.   The pulses may
             be obtained with an electronic timer  that can be pro-
             grammed for short (5 to 60 seconds) ON periods or with
             a conventional  mechanical timer and a special pulse
             circuit.  Figure 3 [a] illustrates a  simple electrical
             pulse circuit for operating the Skinner  Magnelatch
             solenoid valve with a conventional  mechanical timer.
             However, with this simple circuit,  the valve may
             operate unpredictably during brief power interruptions
             or if the timer is manually switched  on  and off too
             fast.  A better circuit incorporating a  time-delay
             relay to provide more reliable valve  operation is
             shown in Figure 3[b].
     7.2.5   Stainless steel  orifice (or short capillary)  - capable
             of maintaining a substantially constant  flow over the
             sampling period (see Figure 4).
     7.2.6   Particulate matter filter - 2 micron  stainless steel
             sintered in-line type (see Figure 4).
     7.2.7   Timer - used for unattended sample  collection.  Capable
             of controlling  pump(s)  and solenoid valve.
7.3  Sample Canister Cleaning (Figure 5)
     7.3.1  Vacuum pump  - capable of evacuating  sample canister(s)
            to  an  absolute  pressure  of <5 mm Hg.
     7.3.2  Manifold -  stainless steel  manifold  with  connections
            for simultaneously  cleaning several  canisters.
     7.3.3  Shut off valve(s)  -  seven required.
     7.3.4  Vacuum gauge -  capable of measuring  vacuum in  the  manifold
            to  an  absolute  pressure  of 5  mm Hg or  less.

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                             T012-8
      7.3.5  Cryogenic trap (2  required)  -  U-shaped  open  tubular trap
             cooled with liquid nitrogen  or argon used to prevent con-
             tamination from back  diffusion of  oil from vacuum pump,
             and to provide clean,  zero air to  sample canister(s).
      7.3.6  Pressure gauge - 0-50 psig (0-345  kPa), to monitor
             zero ai r pressure.
      7.3.7  Flow control  valve -  to  regulate flow of zero air into
             canister(s).
      7.3.8  Humidifier -  water bubbler or  other  system capable of
             providing moisture to the zero air supply.
7.4  Analytical  System (Figure  1)
      7.4.1  FID detector  system - including flow controls for the
             FID fuel  and  air,  temperature  control for the FID, and
             signal  processing  electronics. The FID burner air,
             hydrogen, and helium  carrier flow  rates should be set
             according to  the manufacturer's instructions to obtain an
             adequate FID  response while  maintaining as stable a flame
             as  possible throughout all phases  of the analytical cycle.
      7.4.2  Chart recorder - compatible  with the FID output signal,
             to  record FID response.
      7.4.3  Electronic integrator -  capable of integrating the area
             of  one or more FID response  peaks  and calculating peak
             area corrected for baseline  drift.  If  a separate inte-
             grator and chart recorder are  used,  care must be exer-
             cised to be sure that these  components  do not interfere
             with each other electrically.   Range selector controls
             on  both the integrator and the FID analyzer  may not pro-
             vide accurate range ratios,  so individual calibration
             curves should be prepared for  each range to  be used.
             The integrator should be capable of  marking  the beginning
             and ending of peaks,  constructing  the appropriate base-
             line between  the start and end of  the integration period,
             and calculating the peak area.

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                       T012-9
        Note:  The FID (7.4.1), chart recorder (7.4.2), inte-
        grator (7.4.3), valve heater (7.4.5), and a trap heat-
        ing system are conveniently provided by a standard lab-
        oratory chromatograph and associated integrator.  EPA
        has adapted two such systems for the PDFID method: a
        Hewlett-Packard model 5880 (Hewlett-Packard Corp., Avon-
        dale, PA) and a Shimadzu model  GC8APF (Shimadzu Scientific
        Instruments Inc., Columbia, MD;  see Reference 5).  Other
        similar systems may also be applicable.
7.4.4   Trap - the trap should be carefully constructed from a
        single piece of chromatographic-grade stainless steel
        tubing (0.32 cm O.D, 0.21 cm I.D.) as shown in Figure 6.
        The central  portion of the trap  (7-10 cm) is packed with
        60/80 mesh glass beads, with small glass wool  (dimethyldi-
        chlorosilane-treated) plugs to  retain the beads.  The
        trap must fit conveniently into  the Dewar flask (7.4.9),
        and the arms must be of an appropriate length  to allow
        the beaded portion of the trap'to be submerged below
        the level  of liquid cryogen in the Dewar.  The trap should
        connect directly to the six-port valve, if possible,
        to minimize  line length between  the trap and the FID.  The
        trap must be mounted to allow the Dewar to be  slipped
        conveniently on and off the trap and also to facilitate
        heating of the trap (see 7.4.13).
7.4.5   Six-port  chromatographic valve - Seiscor Model  VIII
        (Seismograph Service Corp., Tulsa, OK), Valco  Model  9110
        (Valco Instruments Co., Houston, TX), or equivalent.
        The six-port valve and as much of the interconnecting
        tubing as  practical  should be located inside an oven or
        otherwise  heated to 80 - 90°C to minimize wall  losses
        or adsorption/desorption in the  connecting tubing.  All
        lines  should be as short as practical.
7.4.6   Multistage pressure regulators - standard two-stage,
        stainless  steel  diaphram regulators with  pressure gauges,
        for helium,  air,  and hydrogen cylinders.
7.4.7   Pressure  regulators  - optional single stage, stainless
        steel, with  pressure gauge, if needed,  to maintain
        constant helium carrier and hydrogen flow rates.

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                       T012-10
7.4.8   Fine needle valve - to adjust  sample  flow  rate  through
        trap.
7.4.9   Dewar flask - to hold liquid  cryogen  to  cool  the  trap,
        sized to contain submerged portion  of trap.
7.4.10  Absolute pressure gauge -  0-450 mm  Hg,(2 mm  Hg  [scale
        divisions indicating units]),  to monitor repeatable
        volumes of sample air through  cryogenic  trap (Wallace
        and Tiernan, Model  61C-ID-0410, 25  Main  Street, Belle-
        ville, NJ).
7.4.11  Vacuum reservoir - 1-2 L capacity,  typically 1  L.
7.4.12  Gas purifiers - gas scrubbers  containing Drierite® or
        silica gel and 5A molecular sieve to  remove  moisture
        and organic impurities in  the  helium, air, and  hydrogen
        gas flows (Alltech Associates, Deerfield,  IL).  Note:
        Check purity of gas purifiers  prior to use by passing
        zero-air through the unit and analyzing  according to
        Section 11.4.  Gas purifiers are clean if  produce
        [contain] less than 0.02 ppmC hydrocarbons.
7.4.13  Trap heating system - chromatographic oven,  hot water,
        or other means to heat the trap to  80° to  90°C.  A simple
        heating source for the trap is a beaker or Dewar  filled
        with water maintained at 80-90°C.  More repeatable types
        of heat sources are recommended, including a temperature-
        programmed chromatograph oven, electrical  heating of
        the trap  itself, or any type of heater that  brings the
        temperature  of the trap up to 80-90°C in 1-2 minutes.
7.4.14  Toggle shut-off valves  (2) - leak free, for vacuum valve
        and  sample valve.
7.4.15  Vacuum pump  - general purpose  laboratory pump capable
        of evacuating the  vacuum reservoir to an appropriate
        vacuum that  allows the  desired  sample volume to  be
        drawn through the  trap.
7.4.16  Vent - to keep  the trap at atmospheric  pressure  during
        trapping  when using  pressurized  canisters.
7.4.17  Rotameter -  to  verify vent flow.

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                             T012-11
      7.4.18  Fine needle  valve  (optional)  - to  adjust  flow  rate of
              sample from  canister  during analysis.
      7.4.19  Chromatographic-grade stainless  steel tubing (Alltech
              Applied Science, 2051 Waukegan Road, Deerfield,  IL, 60015,
              (312) 948-8600)  and stainless steel plumbing fittings -
              for interconnections.  All such  materials in contact
              with the sample, analyte,  or  support gases prior to
              analysis should be stainless  steel or other inert
              metal.  Do not use plastic or Teflon® tubing or  fittings.
7.5   Commercially Available PDFID  System (5)
      7.5.1  A convenient  and cost-effective modular  PDFID system suit-
             able for use  with a conventional  laboratory chromatograph
             is commercially available  (NuTech Corporation,  Model 8548,
             2806 Cheek Road, Durham, NC, 27704,  (919)  682-0402).
      7.5.2  This modular  system contains almost  all  of the  apparatus
             items needed  to convert the chromatograph  into  a  PDFID
             analytical system and  has  been designed  to be readily
             available and easy  to  assemble.
Reagents and Materials
8.1  Gas cylinders of helium and hydrogen - ultrahigh purity grade.
8.2  Combustion air - cylinder containing less than 0.02 ppm hydro-
     carbons, or equivalent air  source.
8.3  Propane calibration standard - cylinder containing 1-100  ppm
     (3-300 ppmC) propane  in air.   The  cylinder assay should be
     traceable to a National Bureau of  Standards  (NBS)  Standard Refer-
     ence Material (SRM) or to  a NBS/EPA-approved  Certified  Reference
     Material (CRM).
8.4  Zero air - cylinder containing less than  0.02 ppmC hydrocar-
     bons.  Zero air may be obtained from a cylinder  of zero-grade
     compressed air scrubbed with Drierite® or silica gel and  5A
     molecular sieve or activated charcoal, or by  catalytic  cleanup

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                                 T012-12
          of  ambient  air.  All zero air should be passed through a liquid
          argon cold  trap for final cleanup, then passed through a hyrdo-
          carbon-free water bubbler (or other device) for humidification.
     8.5  Liquid cryogen - liquid argon (bp -185.7°C) or liquid oxygen,
          (bp -183°C) may be used as the cryogen.  Experiments have shown
          no differences in trapping efficiency between liquid argon and
          liquid oxygen.  However, appropriate safety precautions must be
          taken if liquid oxygen is used.   Liquid nitrogen (bp -195°C)
          should not  be used because it causes condensation of oxygen and
          methane in the trap.
9.  Direct Sampling
     9.1  For direct ambient air sampling,  the cryogenic trapping system
          draws the air sample directly from a pump-ventilated  distribution
          manifold or sample line (see Figure 1).  The connecting line should
          be of small  diameter (1/8"  O.D.)  stainless  steel  tubing and as
          short as possible  to minimize its dead  volume.
     9.2  Multiple analyses  over the  sampling  period  must  be made to  estab-
          lish hourly  or 3-hour NMOC  concentration  averages.
10.  Sample  Collection in  Pressurized  Canister(s)
     For integrated  pressurized  canister sampling,  ambient  air  is sampled
     by a metal  bellows  pump through  a  critical orifice  (to  maintain
     constant  flow), and pressurized  into a clean,  evacuated, Summa®-
     polished  sample canister.   The critical orifice  size is chosen so
     that the  canister is  pressurized to approximately one  atmosphere  above
     ambient pressure, at  a constant  flow rate  over the desired sample
     period.   Two  canisters are  connected in parallel for duplicate samples.
     The canister(s) are then  returned  to the  laboratory for analysis,
     using the PDFID analytical  system.  Collection of ambient air samples
     in pressurized canisters  provides  the  following  advantages:
          o   Convenient integration of ambient samples over a specific
              time period
          o   Capability of remote sampling with  subsequent central
              laboratory analysis
          o   Ability  to ship  and store samples,  if necessary

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                           T012-13
      o  Unattended  sample  collection
      o  Analysis of samples  from  multiple  sites with one analytical
         system                                          ,            ,
      o  Collection  of replicate samples  for  assessment of measurement
         precision
With canister sampling, however, great  care must be  exercised  in
selecting, cleaning, and handling  the  sample  canister(s)  and  sampling
apparatus to avoid losses or contamination  of the  samples.
10.1  Canister Cleanup and Preparation
      10.1.1  All canisters must be clean and free of  any contaminants
              before sample collection.
      10.1.2  Leak test all canisters by pressurizing  them to approxi-
              mately 30 psig [200 kPa (gauge)] with zero  air.  The
              use of the canister cleaning system (see Figure 5)  may
              be  adequate  for this task.  Measure the  final pressure -
              close the canister valve, then check the pressure after
              24  hours.  If leak tight, the pressure should not vary
              more  than +_  2 psig over the 24-hour period.  Note leak
               check result on sampling data sheet, Figure 7.
       10.1.3  Assemble a canister cleaning system, as illustrated in
               Figure  5.  Add cryogen to both the  vacuum pump and zero
               air supply traps.   Connect the canister(s) to the mani-
               fold.  Open  the vent  shut  off  valve and the canister
               valve(s) to  release any  remaining pressure  in the canis-
               ter.   Now close the vent shut  off valve and  open the
               vacuum shut  off valve.   Start  the vacuum pump  and evacuate
               the canister(s) to  <_ 5.0 mm  Hg (for at  least one hour).
               [Note:  On a daily basis  or more often if necessary,  blow-
               out the cryogenic traps  with zero air to remove  any
               trapped water from  previous  canister cleaning  cycles.]
       10.1.4  Close the vacuum  and vacuum  gauge shut  off valves  and
               open  the zero air shut off valve to pressurize the  canis-
               ter(s) with moist zero air to approximately 30 psig [200
               kPa  (gauge)].  If a zero gas generator  system is used,

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                              T012-14
               the  flow  rate may need to be limited to maintain the
               zero air  quality.
       10.1.5   Close the zero  shut off valve and allow canister(s) to
               vent down to atmospheric pressure through the vent shut
               off valve.  Close the vent shut off valve.  Repeat steps
               10.1.3 through  10.1.5 two additional times for a total of
               three (3) evacuation/pressurization cycles for each set of
               canisters.
       10.1.6   As a "blank" check of the canister(s) and cleanup proce-
               dure, analyze the final  zero-air fill of 100% of the
               canisters until  the cleanup system and  canisters are'
               proven reliable.  The check can then be reduced to a
               lower percentage of canisters.   Any canister that does
              not test clean  (compared to direct analysis of humidified
              zero air of less than 0.02 ppmC) should not be utilized.
      10.1.7  The canister is  then re-evacuated to £ 5.0 mm Hg, using
              the canister cleaning system,  and remains in this con-
              dition until use.  Close the  canister valve, remove the
              canister from the canister cleaning  system and cap
              canister connection  with a stainless steel  fitting.  The
              canister is  now  ready for collection of an air sample.
              Attach an  identification  tag to  the  neck  of each
              canister for field notes and chain-of-custody purposes.
10.2  Collection of Integrated Whole-Air Samples
      10.2.1  Assemble the sampling  apparatus  as shown  in Figure  2.
              The connecting lines between the sample pump  and the
              canister(s)  should be  as  short as  possible  to minimize
              their  volume.  A second  canister is  used  when  a  duplicate
              sample  is  desired for  quality assurance (QA)  purposes
              (see  Section 12.2.4).  The small  auxiliary  vacuum pump
              purges the inlet manifold  or lines with a  flow of
              several  L/min to minimize  the sample  residence time.
              The larger metal  bellows pump takes  a small  portion of
              this  sample  to fill  and pressurize the  sample  canister(s).
              Both pumps should  be shock-mounted to minimize vibration.
              Prior to field use,  each sampling  system should  be  leak

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                      T012-15
        tested.   The  outlet  side  of the metal  bellows pump can
        be checked for leaks by attaching  the  0-30 psig pressure
        gauge  to the  canister(s)  inlet via connecting tubing and
        pressurizing  to 2  atmospheres or approximately 29.4 psig.
        If pump  and connecting lines are leak  free pressure should
        remain at +2  psig  for  15  minutes.  To  check the inlet
        side,  plug the sample  inlet and insure that there is no
        flow at  the outlet of  the pump.
10.2.2  Calculate the flow rate needed so  that the canister(s)
        are pressurized to approximately one atmosphere above
        ambient  pressure (2 atmospheres absolute  pressure)
        over the desired sample period, utilizing the following
        equation:
             F = (P)(V)(N)
                  (T)(60)
        where:
             F = flow rate (cm^/min)
             P = final canister pressure  (atmospheres absolute)
              = (Pg/Pa) + 1
             V = volume of the canister (cm3)
             N = number of canisters connected together for
                 simultaneous  sample collection
             T = sample period  (hours)
            Pg = gauge pressure in canister, psig (kPa)
            Pa = standard  atmospheric pressure,  14.7 psig (101 kPa)
        For example,  if one 6-L canister is to be filled to 2
        atmospheres absolute pressure  (14.7 psig) in 3 hours,
        the flow rate would be calculated  as follows:
             F = 2 x  6000  x 1  = 67 cm3/min
                   3 x 60
10.2.3  Select a critical  orifice or hypodermic  needle suitable
        to maintain a substantially constant flow at the cal-
        culated  flow  rate  into the canister(s) over the desired
        sample period.  A  30-gauge hypodermic  needle, 2.5 cm

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                       T012-16
         long,  provides a  flow of  approximately 65 cm3/min with
         the  Metal  Bellows Model MBV-151 pump (see Figure 4).
         Such  a needle  will maintain approximately constant flow
         up to  a canister  pressure of about 10 psig (71 kPa),
         after  which the flow drops with increasing pressure.
         At 14.7 psig (2 atmospheres absolute pressure), the
         flow is about  10% below the original flow.
 10.2.4   Assemble the 2.0 micron stainless steel  in-line particu-
         late filter and position it in front of the critical
         orifice.   A suggested filter-hypodermic needle assembly
         can be fabricated as illustrated in Figure 4.
 10.2.5   Check the  sampling system for contamination by filling
         two evacuated, cleaned canister(s) (See Section 10.1)
         with humidified zero air through the sampling system.
         Analyze the canisters according to Section 11.4.   The
         sampling system is free of contamination  if the canisters
         contain less than 0.02 ppmC hydrocarbons,  similar to
         that of humidified zero air.
 10.2.6   During the system contamination check procedure,  check
         the critical  orifice flow rate  on  the sampling system
         to insure that sample flow rate remains  relatively con-
         stant (+10%)  up to about 2 atmospheres  absolute pressure
         (101 kPa).  Note:   A drop in  the flow rate may occur
        near the end  of the  sampling  period as the canister
        pressure approaches  two atmospheres.
10.2.7  Reassemble the sampling system.  If the inlet sample  line
         is longer than 3 meters,  install  an auxiliary pump to
        ventilate the  sample  line, as  illustrated  in  Figure 2.
10.2.8  Verify that the timer,  pump(s)  and  solenoid  valve  are
        connected  and  operating properly.
10.2.9  Verify that the timer is  correctly  set for the desired
        sample period,  and that the solenoid  valve is closed.
10.2.10 Connect a cleaned, evacuated  canister(s)  (Section  10.1)
        to the non-contaminated  sampling system, by way of  the
        solenoid  valve, for  sample  collection.

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                                 T012-17
          10.2.11  Make sure the solenoid valve is closed.  Open the
                   canister valve(s).  Temporarily connect a small  rotameter
                   to the sample inlet to verify that there is no flow.
                   Note:  Flow detection would indicate a leaking (or open)
                   solenoid valve.  Remove the rotameter after leak de-
                   tection procedure.
          10.2.12  Fill out the necessary information on the Field Data
                   Sheet (Figure 7).
          10.2.13  Set the automatic timer to start and stop the pump
                   or pumps to open and close the solenoid valve at the
                   appropriate time for the intended sample period.
                   Sampling will begin at the pre-determined time.
          10.2.14  After the sample period, close the canister valve(s) and
                   disconnect the canister(s) from the sampling system.
                   Connect a pressure gauge to the canister(s) and briefly
                   open and close the canister valve.  Note the canister
                   pressure on the Field Data Sheet (see Figure 7).  The
                   canister pressure should be approximately 2 atmospheres
                   absolute [1 atmosphere or 101 kPa (gauge)].  Note:  If
                   the canister pressure is not approximately 2 atmospheres
                   absolute (14.7 psig), determine and correct the cause be-
                   fore next sample.  Re-cap canister valve.
          10.2.15  Fill out the identification tag on the  sample canister(s)
                   and complete the  Field Data Sheet as necessary.  Note
                   any activities or special conditions in the area (rain,
                   smoke,  etc.) that may affect the sample contents on the
                   sampling data  sheet.
          10.2.16  Return  the  canister(s) to the analytical system for
                   analysis.
11.  Sample  Analysis
     11.1 Analytical  System Leak  Check
          11.1.1  Before  sample  analysis, the analytical  system is assembled
                    (see Figure 1) and  leak checked.

-------
                            T012-18
       11.1.2   To leak check the analytical system, place the six-port
               gas valve in the trapping position.  Disconnect and cap
               the absolute pressure gauge.  Insert a pressure gauge
               capable of recording up to 60 psig at the vacuum valve
               outlet.
       11.1.3   Attach a valve and a zero air supply to the sample
               inlet port.  Pressurize the system to about 50 psig
               (350 kPa) and close the valve.
       11.1.4   Wait approximately 3 hrs. and re-check pressure.  If
               the pressure did not vary more than +_ 2 psig, the  '
               system is considered leak tight.
       11.1.5   If the system is leak free,  de-pressurize and reconnect
               absolute pressure gauge.
      11.1.6   The analytical  system leak check  procedure needs to
               be performed during  the system checkout,  during a series
               of analysis or if leaks are suspected.   This  should be
               part  of the user-prepared SOP manual  (see Section 12.1).
11.2  Sample Volume  Determination
      11.2.1   The vacuum reservoir and absolute  pressure gauge are
               used  to meter a  precisely repeatable  volume of  sample
               air through  the  cryogenically-cooled  trap,  as follows:
               With  the  sample  valve closed  and the  vacuum valve open,
               the reservoir is  first  evacuated with the vacuum pump
               to a  predetermined pressure  (e.g.,  100  mm Hg).   Then
               the vacuum valve  is  closed and the  sample valve  is
               opened  to  allow sample  air to be drawn  through the
               cryogenic  trap and into  the evacuated reservoir  until
               a  second  predetermined  reservoir pressure is reached
               (e.g.,  300 mm Hg).   The  (fixed) volume  of air thus
               sampled is determined by  the  pressure rise in the
               vacuum  reservoir  (difference  between  the  predetermined
               pressures) as measured  by the absolute  pressure gauge
               (see Section  12.2.1).

-------
                           T012-19
    11.2.2  The sample volume can be calculated by:

                               V
                                s      (P

             where:
                     Vs  =  volume of air sampled (standard cm3)
                    AP  =  pressure difference measured by gauge (mm Hg)
                                                         O
                     Vp  =  volume of vacuum  reservoir  (cm0)
                           usually 1 L
                     Ps  =  standard pressure (760 mm Hg)
             For example,  with  a vacuum  reservoir of 1000 cm3  and  a
             pressure  change  of 200 mm Hg  (100 to 300  mm Hg),  the  volume
             sampled would be 263 cm3.   [Note:   Typical sample volume
             using this procedure is between 200-300 cm3.]
      11.2.3 The sample volume  determination need only be performed  once
             during the system  check-out and shall  be  part  of  the
             user-prepared SOP  Manual  (see Section  12.1).
11.3  Analytical  System Dynamic  Calibration
      11.3.1  Before sample analysis, a  complete  dynamic calibration
              of the analytical  system  should be  carried out at five  or
              more concentrations  on  each range  to  define  the calibra-
              tion curve.   This  should  be carried out  initially and
              periodically thereafter [may be done  only once during
              a series of  analyses].   This should be part  of the
              user-prepared SOP Manual  (See Section 12.1).   The
              calibration  should be verified with two or three-point
              calibration checks (including zero) each day the analyt-
              ical system is  used to analyze samples.
      11.3.2  Concentration standards of propane are used to calibrate
              the analytical  system.  Propane calibration standards
              may be obtained directly from  low concentration  cylinder
              standards or by dilution  of high concentration cylinder

-------
                       T012-20
         standards  with zero  air  (see Section 8.3).  Dilution
         flow rates must be measured accurately, and the combined
         gas  stream must be mixed thoroughly for successful cali-
         bration  of the analyzer.  Calibration standards should
         be sampled directly  from a vented manifold or tee.  Note:
         Remember that  a propane NMOC concentration in ppmC is
         three times the volumetric concentration in ppm.
 11.3.3   Select one or more combinations of the following parameters
         to provide the desired range or ranges (e.g., 0-1.0 ppmC
         or 0-5.0 ppmC):  FID attenuator setting, output voltage
         setting, integrator  resolution (if applicable), and sample
         volume.  Each individual  range should be calibrated sep-
         arately and should have a separate calibration curve.
         Note: Modern GC integrators may provide automatic ranging
         such that  several  decades of concentration may be covered
         in a single range.  The user-prepared SOP manual  should
         address variations applicable to a specific system design
         (see Section 12.1).
11.3.4  Analyze each calibration  standard three times  according
        to the procedure in  Section  11.4.  Insure  that flow
         rates, pressure gauge start  and stop  readings, initial
        cryogen liquid level  in the  Dewar, timing,  heating,  inte-
        grator settings,  and  other  variables  are the  same  as
        those that  will be used during  analysis  of  ambient
        samples.  Typical  flow  rates  for the  gases  are:  hydrogen,
        30 cm^/minute; helium carrier,  30 cm^/minute;  burner
        air,  400  cm3/minute.
11.3.5  Average the three  analyses for  each concentration  standard
        and plot  the  calibration  curve(s)  as  average integrated peak
        area  reading  versus concentration in  ppmC.  The  relative
        standard  deviation for  the three  analyses should be less

-------
                            T012-21
              than 3% (except  for zero  concentration).  Linearity should
              be  expected;  points that  appear to deviate abnormally
              should be repeated. Response  has been  shown to  be linear
              over a wide  range  (0-10,000  ppbC).   If  nonlinearity is
              observed, an  effort should be  made to identify and correct
              the problem.   If the problem cannot  be  corrected, addi-
              tional points in the nonlinear region may be needed to
              define the calibration  curve adequately.
11.4  Analysis Procedure
      11.4.1  Insure the analytical system has  been assembled  properly,
              leaked checked,  and properly calibrated through  a dynamic
              standard calibration.   Light the  FID detector and allow to
              stabilize.
      11.4.2  Check and adjust the helium  carrier  pressure to  provide the
              correct carrier  flow rate for  the  system.  Helium is used
              to  purge residual  air  and methane from  the trap  at the
              end of the sampling phase and  to  carry  the re-volatilized
              NMOC from the trap into the  FID.   A  single-stage auxiliary
              regulator between  the  cylinder and the  analyzer  may not
              be  necessary, but  is recommended  to  regulate the helium
              pressure better  than the multistage  cylinder regulator.
              When an auxiliary  regulator  is used, the  secondary  stage
              of  the two-stage regulator must be set  at a  pressure
              higher than the  pressure setting  of  the single-stage
              regulator.  Also check  the FID hydrogen and  burner  air
              flow rates (see  11.3.4).
     11.4.3   Close the sample valve  and open the  vacuum  valve to
              evacuate the vacuum reservoir  to a specific  predetermined
              value (e.g., 100 mm Hg).
     11.4.4   With the trap at room  temperature,  place the  six-port
              valve in the inject position.
     11.4.5   Open the sample  valve  and adjust the sample  flow rate
              needle valve for an appropriate trap flow of 50-100
              cm3/min.  Note:  The flow will  be lower later,  when  the
              trap  is cold.

-------
                        T012-22
 11.4.6   Check  the sample canister  pressure  before  attaching  it
          to the analytical  system and  record on  Field  Data
          Sheet  (see Figure  7).   Connect  the  sample  canister or
          direct sample  inlet  to  the six-port valve, as shown  in
          Figure 1.   For a canister, either the canister valve
          or an  optional  fine  needle valve installed between the
          canister  and the vent is used to adjust the canister
          flow rate  to a value  slightly higher than the trap
          flow rate  set  by the  sample flow rate needle valve.
          The excess  flow exhausts through the vent, which
          assures that the sample air flowing through the trap
          is at  atmospheric  pressure.  The vent is connected to
          a  flow indicator such as a rotameter as an indication of
          vent flow to assist in  adjusting the flow control
          valve.  Open the canister valve and adjust the canister
          valve or the sample flow needle valve to obtain a
         moderate vent  flow as indicated by the rotameter.  The
         sample flow rate will be lower (and hence the vent
         flow rate will  be higher)  when the the trap is cold.
11.4.7   Close the sample valve and  open the vacuum valve (if
         not already open) to evacuate the vacuum reservoir.
         With the six-port valve  in  the inject  position and the
         vacuum valve open,  open  the sample valve for  2-3 minutes
         [with both valves open,  the pressure reading  won't
         change] to flush and condition the inlet lines.
11.4.8   Close the sample valve and  evacuate  the  reservoir to
         the predetermined sample starting pressure (typically
         100 mm Hg) as  indicated  by  the absolute  pressure gauge.
11.4.9   Switch  the six-port valve to  the sample  position.
11.4.10  Submerge the trap in the cryogen.  Allow a  few minutes
         for the trap to cool  completely  (indicated  when  the
         cryogen stops boiling).  Add  cryogen to  the initial
         level  used during system dynamic calibration.   The level
         of the  cryogenic liquid  should  remain  constant with
         respect to the  trap and  should  completely  cover  the
         beaded  portion  of the trap.

-------
                        T012-23
11.4.11   Open the sample valve  and  observe  the  increasing pressure
          on the pressure gauge.   When  it  reaches the  specific  pre-
          determined pressure (typically  300 mm  Hg)  representative
          of the desired sample  volume  (Section  11.2), close  the
          sample valve.
11.4.12   Add a little cryogen or elevate the Dewar  to raise  the
          liquid level to a point slightly higher  (3-15 mm) than
          the initial level at the beginning of  the  trapping.
          Note:  This insures that organics do not bleed from the
          trap and are counted as part  of the NMOC peak(s).
11.4.13   Switch the 6-port valve to the inject  position, keeping
          the cryogenic  liquid on the trap until the methane  and
          upset peaks have deminished (10-20 seconds).  Now close
          the canister valve to conserve the remaining sample in
          the canister.
11.4.14   Start the  integrator and remove the Dewar flask containing
          the cryogenic  liquid from the trap.
11.4.15   Close the  GC oven door and allow the GC oven (or alter-
          nate trap  heating system) to heat the trap  at a predeter-
          mined rate (typically, 30°C/min) to 90°.  Heating the trap
          volatilizes the  concentrated NMOC such that the FID pro-
          duces integrated peaks.  A uniform trap temperature rise
          rate  (above 0°C) helps to reduce  variability and facili-
          tates more accurate correction  for the moisture-shifted
          baseline.   With  a  chromatograph  oven  to heat the trap,
          the following  parameters  have  been  found  to be acceptable:
          initial  temperature,  30°C; initial time,  0.20 minutes
           (following start of the  integrator);  heat rate, 30°/minute;
          final temperature,  90°C.
 11.4.16  Use the same  heating  process  and  temperatures  for  both
           calibration and sample analysis.   Heating the  trap too
           quickly may cause  an  initial  negative response that
           could hamper accurate integration.  Some  initial exper-
           imentation may be necessary  to determine  the optimal
           heating procedure  for each system.  Once  established,
           the procedure should  be consistent for  each analysis
           as outlined in the user-prepared SOP  Manual.

-------
                        T012-24
11.4.17   Continue the integration  (generally,  in  the  range  of
          1-2 minutes  is adequate)  only  long enough  to include
          all of the organic  compound  peaks and  to establish the
          end point FID baseline, as  illustrated in  Figure 8.
          The integrator should be  capable of marking  the begin-
          ning and ending  of  peaks, constructing the appropriate
          operational  baseline  between the start and end of  the
          integration  period, and calculating the  resulting
          corrected peak area.   This  ability is  necessary because
          the moisture in  the sample,  which is  also  concentrated
          in the trap,  will cause a slight positive  baseline
          shift.  This  baseline shift  starts as  the  trap warms
          and continues until all of  the moisture  is swept from
          the trap, at  which time the  baseline  returns  to its
          normal  level.  The  shift  always continues  longer than
          the ambient  organic peak(s).   The integrator  should be
          programmed to correct for this shifted baseline by
          ending the integration at a  point after  the  last NMOC
          peak and prior to the return of the shifted  baseline to
          normal  (see  Figure 8)  so that  the calculated  operational
          baseline effectively  compensates for  the water-shifted
          baseline. Electronic  integrators either do this auto-
          matically or  they should  be  programmed to  make this cor-
          rection.  Alternatively, analyses of  humidified zero air
          prior to sample  analyses  should be performed  to determine
          the water envelope and the  proper blank  value for
          correcting the ambient air  concentration measurements
          accordingly.   Heating  and flushing of  the  trap should
          continue after the  integration period  has  ended to
          insure all water has  been removed to  prevent  buildup of
          water in the  trap.  Therefore, be sure that  the 6-port
          valve remains in the  inject  position  until all moisture
          has purged from  the trap  (3  minutes or longer).

-------
                                T012-25
         11.4.18   Use the dynamic calibration curve (see Section 11.3)
                  to convert the integrated peak area reading into
                  concentration units (ppmC).  Note that the NMOC peak
                  shape may not be precisely reproducible due to vari-
                  ations  in heating the trap, but the total NMOC peak
                  area should be reproducible.
         11.4.19   Analyze each canister sample at least twice and report
                  the average NMOC concentration.  Problems during an
                  analysis occasionally will cause erratic or incon-
                  sistent results.   If the first two analyses do not
                  agree within +_ 5%  relative standard deviation (RSD),
                  additional analyses should be made to identify in-
                  accurate measurements and produce a more accurate
                  average  (see also  Section 12.2.).
12.  Performance  Criteria  and Quality  Assurance
     This section summarizes  required  quality assurance measures and pro-
     vides guidance  concerning  performance criteria that should be achieved
     within each  laboratory.
     12.1   Standard Operating  Procedures  (SOPs)
            12.1.1  Users  should  generate  SOPs describing  and  documenting
                    the  following  activities  in their  laboratory:   (1)
                    assembly,  calibration,  leak check, and operation  of the
                    specific  sampling system and  equipment used;  (2)  prepara-
                    tion,  storage,  shipment,  and  handling  of  samples;  (3)
                    assembly,  leak-check,  calibration, and operation  of the
                    analytical  system, addressing  the  specific equipment used;
                    (4)  canister  storage and  cleaning; and (5) all  aspects of
                    of data recording and  processing,  including  lists of
                    computer hardware and software used.
            12.1.2  SOPs should provide specific  stepwise  instructions and
                    should be readily available  to, and  understood by, the
                    laboratory personnel  conducting the  work.

-------
                            T012-26
12.2  Method Sensitivity,  Accuracy, Precision  and  Linearity
     12.2.1  The sensitivity and  precision  of  the  method  is proportional
             to the sample volume.   However, ice formation  in  the
             trap may reduce or stop the  sample flow  during trapping
             if the sample volume exceeds 500  cm3.  Sample  volumes
             below about 100-150  cm3 may  cause increased  measurement
             variability due to dead volume in lines  and  valves.  For
             most typical  ambient NMOC concentrations, sample  volumes
             in the range  of 200-400 cm3  appear to be appropriate.
             If a response  peak obtained with a 400 cm3 sample is
             off scale or  exceeds the calibration range, a  second
             analysis can  be carried  out with a smaller volume.  The
             actual  sample  volume used need not be accurately known
             if it  is precisely repeatable during both calibration
             and  analysis.   Similarly, the actual  volume of the
             vacuum  reservoir need  not be accurately known.  But the
             reservoir volume should be matched to the pressure
             range  and resolution of the absolute pressure gauge so
             that the measurement of the pressure  change in the reser-
             voir, hence the sample volume,  is  repeatable within 1%.
             A  1000  cm3 vacuum  reservoir and a  pressure change of
             200 mm  Hg, measured with the specified pressure gauge,
             have provided  a sampling precision of  +_ 1.31 cm3.  A
             smaller volume reservoir may be used  with a greater
            pressure change to accommodate  absolute pressure gauges
            with lower resolution,  and  vice versa.
    12.2.2  Some FID detector systems associated with laboratory
            chromatographs may have autoranging.   Others may
            provide attenuator control  and  internal  full-scale
            output voltage selectors,  an appropriate combination
            should be chosen so that an  adequate output  level  for
            accurate integration  is obtained down  to  the  detection
            limit; however, the electrometer or integrator must  not
            be driven into saturation at  the upper end  of the
            calibration.   Saturation of  the electrometer  may be
            indicated by flattening of the  calibration  curve at

-------
                                T012-27
                 high concentrations.  Additional adjustments of range
                 and sensitivity can be provided by adjusting the sample
                 volume used, as discussed in Section 12.2.1.
          12.2.3  System linearity has been documented (6) from 0 to 10,000
                 ppbC.
          12.2.4  Some organic compounds contained in ambient air are
                 "sticky" and may require repeated analyses before they
                 fully appear in the FID output.  Also, some adjustment
                 may have to be made in the integrator off time setting
                 to accommodate compounds that reach the FID late in the
                 analysis cycle.  Similarly, "sticky" compounds from
                 ambient samples or from contaminated propane standards
                 may temporarily contaminate the analytical system and
                 can affect  subsequent analyses.  Such temporary contam-
                 ination can usually be removed  by repeated analyses of
                 humidified  zero air.
          12.2.5  Simultaneous collection of duplicate samples decreases
                 the possibility of lost measurement data from samples
                 lost due to leakage or contamination in either of the
                 canisters.  Two (or more) canisters can be filled simul-
                 taneously  by connecting them in parallel (see Figure 2(a))
                 and selecting an appropriate flow rate to accommodate
                 the number of canisters (Section 10.2.2).  Duplicate (or
                 replicate)  samples  also allow assessment of measurement
                 precision  based on  the differences between duplicate samples
                 (or the  standard deviations among replicate samples).
13.  Method Modification
     13.1   Sample Metering  System
          13.1.1  Although  the vacuum reservoir  and absolute  pressure  gauge
                 technique  for metering the  sample volume during  analysis is
                 efficient  and  convenient, other techniques  should work  also.
          13.1.2   A constant sample  flow could be established with  a vacuum
                  pump  and  a critical  orifice, with the  six-port valve being
                  switched  to the  sample  position for  a  measured time  period.

-------
                             T012-28
              A gas volume meter,  such  as  a  wet  test meter,  could
              also be used to measure the  total  volume  of  sample air
              drawn through the  trap.   These alternative techniques
              should be  tested and  evaluated as  part of a  user-prepared
              SOP  manual.
 13.2   FID  Detector System
      13.2.1   A variety  of FID detector systems  should be  adaptable to
              the  method.
      13.2.2   The  specific  flow  rates and necessary modifications for
              the  helium carrier for any alternative FID instrument
              should  be  evaluated prior to use as part of the user-
              prepared SOP manual.
13.3  Range
     13.3.1   It may be possible to increase the sensitivity of the
             method by increasing the  sample volume.   However,
             limitations may arise such as plugging of the trap by ice.
     13.3.2  Any attempt to increase sensitivity should be evaluated
             as part of  the user-prepared  SOP manual.
13.4  Sub-Atmospheric Pressure Canister Sampling
     13.4.1  Collection  and analysis of canister air  samples at sub-
             atmospheric pressure  is also  possible  with minor modifi-
             cations to  the sampling and analytical procedures.
     13.4.2  Method TO-14, "Integrated  Canister  Sampling for Selective
             Organics:   Pressurized and Sub-atmospheric Collection
             Mechanism,"  addresses sub-atmospheric pressure canister
             sampling.   Additional  information can  be  found  in  the
             literature  (11-17).

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                                  T012-29

 1.  Uses, Limitations, and Technical  Basis of Procedures for Quantifying
     Relationships Between Photochemical  Oxidants and Precursors, EPA-
     450/2-77-21a, U.S. Environmental  Protection Agency, Research Triangle
     Park, NC, November 1977.

 2.  Guidance for Collection of Ambient Non-Methane Organic Compound
     TNMOC) Data for Use in 1982 Ozone SIP Development. EPA-450/4-80-011,
     U.S. Environmental Protection Agency, Research Triangle Park, NC,
     June 1980.

 3.  H. B. Singh, Guidance for the Collection and Use of Ambient Hydrocarbons
     Species Data in Development of Ozone Control Strategies, EPA-450/480-008.
     U.S. Environmental Protection Agency, Research Triangle Park, NC,
     April 1980.

 4.  R. M. Riggin, Technical Assistance Document for Sampling and Analysis
     of Toxic Organic Compounds in Ambient Air, EPA-600/483-027, U.S.
     Environmental Protection Agency,  Research Triangle Park, NC, 1983.

 5.  M. J. Jackson, et^ _al_., Technical  Assistance Document for Assembly and
     Operation of the Suggested Preconcentration Direct Flame lonization
     Detection (PDFID) Analytical  System, publication scheduled for late
     1987; currently available in  draft form from the Qualilty Assurance
     Division, MD-77, U.S. Environmental  Protection Agency, Research
     Triangle Park, NC 27711.

 6.  R. K. M. Jayanty, et^ aj_., Laboratory Evaluation of Non-Methane Organic
     Carbon Determination in Ambient Air  by Cryogenic Preconcentration and
     Flame lonization Detection, EPA-600/54-82-019, U.S. Evironmental  Protec-
     tion Agency, Research Triangle Park, NC, July 1982.

 7.  R. D. Cox, jet^ ^1_., "Determination of Low Levels of Total  Non-Methane
     Hydrocarbon Content in Ambient Air", Environ. Sci. Techno!., JUS (1):57.
     1982.

 8. F.  F. McElroy, et^ aj_., A Cryogenic Preconcentration - Direct FID (PDFID)
     Method for Measurement of NMOC in the Ambient Air, EPA-600/4-85-063,
     U.S. Environmental  Protection Agency, Research Triangle Park, NC,
     August 1985.

 9.  F. W. Sexton, et^ jjl_., A Comparative  Evaluation of Seven Automated
     Ambient Non-Methane Organic Compound Analyzers, EPA-600/5482-046,
     U.S. Environmental  Protection Agency, Research Triangle Park, NC,
     August 1982.

10.  H. G. Richter, Analysis of Organic Compound Data Gathered During  1980
     in Northeast Corridor Cities, EPA-450/4-83-017, U.S. Environmental
     Protection Agency, Research Triangle Park, NC, April 1983.

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                                 T012-30

11.  Cox, R. D. "Sample Collection  and  Analytical Techniques  for Volatile
     Organics in Air,"  presented  at APCA  Speciality  Conference, Chicago, II
     March 22-24, 1983.

12.  Rasmussen, R.  A. and  Khalil, M.A.K.  "  Atmospheric Halocarbons:
     Measurements and Analyses  of Selected  Trace Gases," Proc. NATO ASI on
     Atmospheric Ozone, 1980, 209-231.

13.  Oliver, K. D., Pleil  J.D.  and  McClenny, W.A. "Sample  Intergrity of
     Trace Level  Volatile  Organic Compounds  in Ambient Air Stored  in
     "SUMMA®" Polished  Canisters,"  accepted  for publication in Atmospheric
     Environment as of  January  1986.  Draft  available from W. A. McClenny,
     MD-44, EMSL, EPA,  Research Triangle  Park, NC 27711.

14.  McClenny, W. A. Pleil  J.D. Holdren,  J.W.; and Smith,  R.N.; 1984.
     " Automated Cryogenic Preconcentration  and Gas  Chromatographic
     Determination  of Volatile  Organic  Compounds," Anal. Chem. 56:2947.

15.  Pleil, J. D. and Oliver, K.  D.,  1985,  "Evaluation of  Various  Config-
     urations of Nafion Dryers:  Water  Removal from  Air Samples Prior to
     Gas Chromatographic Analysis".  EPA  Contract No. 68-02-4035.

16.  Oliver, K. D.; Pleil, and  McClenny,  W.  A.; 1986.  "Sample Integrity
     of Trace Level Volatile Organic  Compounds in Ambient  Air Stored in
     Summa® Polished Canisters,"  Atmospheric Environ.  20:1403.

17.  Oliver, K. D.  Pleil,  J. D.,  1985,  "Automated Cryogenic Sampling and
     Gas Chromatographic Analysis of  Ambient Vapor-Phase Organic Compounds:
     Procedures and Comparison  Tests,"  EPA  Contract  No. 68-02-4035,
     Research Triangle  Park, NC,  Northrop Services,  Inc. - Environmental
     Sciences.

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                                          T012-31
                                                            PRESSURE
                                                           REGULATOR
                            ABSOLUTE
                          PRESSURE GAUGE
                VACUUM
                 VALVE
                VACUUM
                 PUMP
SAMPLE
 VALVE
                          VACUUM
                         RESERVOIR
         FINE
        NEEDLE
        VALVE
     (SAMPLE FLOW
     ADJUSTMENT)
                                                                    He
                                                             GAS
                                                           PURIFIER
                    VENT
         PRESSURIZED (EXCESS)
          CANISTER
           SAMPLE
 CANISTER
   VALVE
CANSITER
                 DIRECT AIR SAMPLING
                                                                            DEWAR
                                                                            FLASK

                                                                            GLASS
                                                                            BEADS
                       ROTAMETER
                              CRYOGENIC
                             TRAP COOLER
                             (LIQUID ARGON)
                                     PRESSURE
                              GAS    REGULATOR
                             PURIFIER
              (OPTIONAL FINE
              NEEDLE VALVE)
                                          INTEGRATOR
                                           RECORDER
            FIGURE 1.  SCHEMATIC OF ANALYTICAL SYSTEM FOR
                         NMOC-TWO SAMPLING MODES

-------
                     T012-32
SAMPLE
   IN
      CRITICAL
      ORIFICE
AUXILIARY     IN
 VACUUM
  PUMP
                             TIMER
SOLENOID
 VALVE
             METAL
            BELLOWS
             PUMP
                                          PRESSURE
                                           GAUGE
                                    CANISTER(S)
  FIGURE 2. SAMPLE SYSTEM FOR AUTOMATIC COLLECTION
           OF 3-HOUR INTEGRATED AIR SAMPLES

-------
                                             T012-33
                         TIMER
                         SWITCH
                                         100K
                                                    RED
                    115 VAC
                                    40^fd, 450 V DC
                                       R2 100K
                                                   BLACK
                           PUMP'1
4LVfd, 450 V DC  o2

               WHITE
           COMPONENTS
           Capacitor Ci and C2 - 40 u(, 450 VDC (Sprague Atom* TVA 1712 or equivalent)
           Resister RI and Rj - 0.5 watt. 5% tolerance
           Diode DI and 02 • 1000 PRV, 2.5 A (RCA. SK 3081 or equivalent)
                                                                MAGNELATCH
                                                                 SOLENOID
                                                                   VALVE
           FIGURE 3[a].  SIMPLE CIRCUIT FOR  OPERATING MAGNELATCH VALVE
      TIMER
     SWITCH
         O
115 VAC
        COMPONENTS
        Bridge Rectifier - 200 PRV, 1.5 A (RCA. SK 3105 or equivalent)
        Oiode D-i and 02 - 1000 PRV. 2.5 A (RCA, SK 3081 or equivalent)
        Capacitor Ci - 200 ul, 250 VDC (Sprague Atom* TVA 1528 or equivalent)
        Capacitor Cz - 20 uf, 400 VOC Non-Polarized (Sprague Atom* TVAN 1652 or equivalent)
        Relay - 10,000 ohm coil, 3.5 ma (AMF Potter and Brumfield, KCP 5, or equivalent)
        Resister RI and KZ • 0-5 watt. 5% tolerance
                                             MAGNELATCH
                                              SOLENOID
                                               VALVE
                                20 uf
                                400 Voll
                                  NON-POLARIZED
         FIGURE 3[b],   IMPROVED CIRCUIT  DESIGNED TO HANDLE POWER INTERRUPTIONS
              FIGURE 3.  ELECTRICAL PULSE CIRCUITS FOR DRIVING
                             SKINNER MAGNELATCH SOLENOID VALVE
                             WITH  A MECHANICAL TIMER

-------
                           T012-34
                   'F' SERIES COMPACT, INLINE FILTER
                   W/2 urn SS SINTERED ELEMENT
                     FEMALE CONNECTOR, 0.25 in O.D. TUBE TO
                     0.25 in FEMALE NPT
                    HEX NIPPLE, 0.25 in MALE NPT BOTH ENDS
                  30 GAUGE x 1.0 in LONG HYPODERMIC
                  NEEDLE (ORIFICE)
                      FEMALE CONNECTOR, 0.25 in O.D. TUBE TO
                      0.25 in FEMALE NPT
                  THERMOGREEN LBI 6 mm (0.25 in)
                  SEPTUM (LOW BLEED)
                    0.25 in PORT CONNECTOR W/TWO 0.25 in NUTS
FIGURE 4. FILTER AND  HYPODERMIC NEEDLE
            ASSEMBLY FOR SAMPLE INLET FLOW
            CONTROL

-------
                                   T012-35
                                           3-PORT
                                                              ZERO AIR
                                                              SUPPLY

                                                                V
GAS
VALVE
-KM O
l^\| V,.
VENT VALVE /
CHECK VALVE
^
^
T

u




s
CRYOGENIC
'TRAP
VACUUM   VACUUM PUMP
 PUMP    SHUT OFF VALVE   VENT VALVE
ZERO AIR
SUPPLY
                 VENT SHUT OFF
                 VALVE
      VACUUM SHUT OFF
      VALVE
       VENT
                                                           VENT SHUT OFF
                                                           VALVE
                                                          HUMIDIFIER
                       CRYOGENIC
                       TRAP

                                         VACUUM GAUGE
                                         SHUT OFF VALVE
                                              — PRESSURE
                                                 GAUGE
                                                           ZERO SHUT OFF
                                                           VALVE
                                               FLOW
                                               CONTROL
                                               VALVE
            VENT SHUT OFF
            VALVE

                                   A
                                                          MANIFOLD
                                    J_]H CANISTER VALVE
                               SAMPLE CANISTERS
               FIGURE 5. CANISTER CLEANING SYSTEM

-------
                             T012-36
       TUBE LENGTH: -30 cm
             O.D.: 0.32 cm
              I.D.: 021 cm
CRYOGENIC LIQUID LEVEL'
   60/80 MESH GLASS BEADS
                           -GLASS WOOL-
                                          ~13 cm
                           (TO FIT DEWAR)
      FIGURE 6. CRYOGENIC SAMPLE TRAP DIMENSIONS

-------
GENERAL  INFORMATION:
                          PRESSURIZED CANISTER SAMPLING DATA SHEET
PROJECT:
SITE:
LOCATION:
MONITOR  STATION NUMBER:
PUMP SERIAL NUMBER:
        OPERATOR:	
        ORIFICE IDENTIFICATION:
        FLOW RATE:
        CALIBRATED BY:
        LEAK CHECK
                                                   Pass
                                        Fail
FIELD DATA:
Date




Canister
Serial
Number




Sample
Number




Sample Time
Start




Stop




Average Atmospheric Conditions
Temperature




Pressure




Relative Humidity




Canister pressure
Final , Laboratory










Comments





                                                                                                      o
                                                                                                      I—»
                                                                                                      ro
                                                                                                      CO
Date
Title
Signature
                 FIGURE 7.  EXAMPLE SAMPLING DATA SHEET

-------
                              T012-38
        NMOC
        PEAK
w
w
O
D-
(0
W
DC
  START
INTEGRATION
                         END
                      INTEGRATION
                                 CONTINUED HEATING
                                     OF TRAP
                                 WATER-SHIFTED
                                   BASELINE
1
                                          t
           OPERATIONAL BASELINE
         CONSTRUCTED BY INTEGRATOR
        TO DETERMINE CORRECTED AREA
                              NORMAL BASELINE
                              TIME (MINUTES)
       FIGURE 8. CONSTRUCTION OF OPERATIONAL BASELINE
                  AND CORRESPONDING CORRECTION OF
                  PEAK AREA

-------
                                                               Revision 1.0
                                                               June, 1988
                                METHOD TO-13
           THE DETERMINATION OF BENZO(a)PYRENE [B(a)P] AND OTHER
     POLYNUCLEAR AROMATIC HYDROCARBONS (PAH's) IN AMBIENT AIR USING GAS
              CHROMATOGRAPHIC (GC) AND HIGH PERFORMANCE LIQUID
                      CHROMATOGRAPHIC (HPLC) ANALYSIS

                                  OUTLINE

 I.  Scope
 2.  Applicable Documents
 3.  Summary of Method
 4*  Significance
 5.  Definitions
 6.  Interferences
 7.  Safety
 8.  Apparatus
     8.1  Sample Collection
     8.2  Sample Clean-up and Concentration
     8.3  Sample Analysis
          8.3.1  Gas Chromatography with Flame lonization Detection
          8.3.2  Gas Chromatography with Mass Spectroscopy Detection
                 Coupled with Data Processing System (GC/MS/DS)
          8.3.3  High Performance Liquid Chromatography System
 9.  Reagents and Materials
     9.1  Sample Collection
     9.2  Sample Clean-up and Concentration
          9.2.1  Soxhlet Extraction
          9.2.2  Solvent Exchange
          9.2.3  Column Clean-up
     9.3  Sample Analysis
          9.3.1  Gas Chromatography Detection
          9.3.2  High Performance Liquid Chromatography Detection
10.  Preparation of Sampling Filter and  Adsorbent
     10.1  Sampling Head Configuration
     10.2  Glass Fiber Filter Preparation
     10.3  XAD-2 Adsorbent Preparation
     10.4  PUF Sampling Cartridge Preparation
11.  Sample Collection
     11.1  Description of Sampling Apparatus
     11.2  Calibration of Sampling System
           11.2.1  Calibration of Flow Rate Transfer Standard
           11.2.2  Initial  Multi-point Calibration of High Volume Sampling System
                   Utilizing Flow Rate Transfer Standard
           11.2.3  Single Point  Audit of the High Volume Sampling System
                   Utilizing Flow Rate Transfer Standard
     11.3  Sample Collection
12.  Sample Clean-up and Concentration
     12.1  Sample Identification
     12.2  Soxhlet Extraction and Concentration
     12.3  Solvent Exchange
     12.4  Sample Clean-up by Solid Phase Exchange and  Concentration
           12.4.1  Method 610 Clean-up Procedure
           12.4.2  Lobar Prepacked Column Procedure

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                              OUTLINE (cont'd)
13.  Gas Chromatography (GC)  with Flame lonization (FI)  Detection
     13.1  Analytical  Technique
     13.2  Analytical  Sensitivity
     13.3  Analytical  Assembly
     13.4  GC Calibration
           13.4.1  External  Standard Calibration Procedure
           13.4.2  Internal  Standard Calibration Procedure
     13.5  Retention Time Window Determination
     13.6  Sample Analysis
           13.6.1  Sample Injection
           13.6.2  Area Counts and Peak Height
           13.6.3  Analyte Identification
           13.6.4  Analyte Quantification
14.  Gas Chromatography (GC)  with Mass Spectroscopy (MS) Detection
     14.2  Analytical  System
     14.2  Operation Parameters
     14.3  Calibration Techniques
           14.3.1  External  Standard Calibration
           14.3.2  Internal  Standard Calibration
     14.4  Sample Analysis
           14.4.1  Preliminary Screening by GC/FID
           14.4.2  Sample Injection
           14.4.3  Area Counts
           14.4.4  Analyte Identification
           14.4.5  Spectrum Comparison
           14.4.6  Analyte Quantification
     14.5  GC/MS Performance Tests
           14.5.1  Daily DFTPP Tuning
           14.5.2  Daily 1-point Initial Calibration Check
           14.5.3  12-hour Calibration Verification
15.  High Performance Lliquid Chromatography (HPLC) Detection
     15.1  Introduction
     15.2  Solvent Exchange to Acetonitrile
     15.3  HPLC Assembly
     15.4  HPLC Calibration
           15.4.1  Stock Standard Solution
           15.4.2  Storage of Stock Standard Solution
           15.4.3  Replacement of Stock Standard  Solution
           15.4.4  Calibration Standards
           15.4.5  Analysis of Calibration Standards
           15.4.6  Lingar Response
           15.4.7  Daily Calibration
     15.5  Sample Analysis
     15.6  HPLC System Performance
     15.7  HPLC Method Modification
16.  Quality Assurance/Quality Control  (QA/QC)
     16.1  General System QA/QC
     16.2  Process, Field and Solvent  Blanks
     16.3  Gas Chromatography with  Flame lonization Detection
     16.4  Gas Chromatography with  Mass Spectroscopy Detection
     16.5  High Performance Liquid  Chromatography Detection

-------
                              OUTLINE (cont'd)
17.  Calculations
     17.1  Sample Volume
     17.2  Sample Concentration
           17.2.1  Gas Chromatography with Flame lonization Detection
           17.2.2  Gas Chromatography with Mass Spectroscopy Detection
           17.2.3  High Performance Liquid Chromatography Detection
     17.3  Sample Conversion from ng/m3 to ppbv
18.  Bibliography

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-------
                           METHOD TO-13
           THE  DETERMINATION  OF  BENZO(a)PYRENE [B(a)P] AND OTHER
     POLYNUCLEAR AROMATIC  HYDROCARBONS  (PAHs)  IN AMBIENT AIR USING GAS
             CHROMATOGRAPHIC  (GC) AND HIGH  PERFORMANCE LIQUID
                      CHROMATOGRAPHIC (HPLC) ANALYSIS

1.  Scope
     1.1  Polynuclear aromatic  hydrocarbons (PAHs)  have  received  increased
          attention in recent years  in  air  pollution  studies  because  some
          of these compounds  are highly carcinogenic  or mutagenic.   In  par-
          ticular, benzo[a]pyrene (B[a]P) has  been  identified as  being
          highly carcinogenic.   To  understand  the  extent  of  human exposure
          to B[a]Ps and other PAHs, a  reliable sampling  and  analytical  method
          has been established.  This document describes  a sampling  and
          analysis procedure  for B[a]P  and  other PAHs involving a combination
          quartz filter/adsorbent cartridge with subsequent  analysis by gas
          chromatography (GC) with  flame ionization (FI)  and mass spectrometry
          (MS) detection (GC/FI and 6C/MS)  or high resolution liquid chroma-
          tography (HPLC).  The analytical  methods are a modification of EPA
          Test Method 610 and 625,  Methods  for Organic Chemical Analysis of
          Municipal and Industrial  Wastewater, and Methods 8000, 8270, and
          8310, Test Methods for Evaluation of Solid Waste.
     1.2  Fluorescence methods were among the very first methods used for
          detection of B[a]P and other PAHs as a carcinogenic constituent
          of coal tar  (1-7).  Fluorescent methods are capable of measuring
           subnanogram  quantities of PAHs,  but tend to be fairly non-selective.
          The  normal  spectra obtained tended to be intense and lacked  reso-
           lution.  Efforts to  overcome this difficulty led to the use  of
           ultraviolet  (UV) absorption spectroscopy as the detection method
           coupled  with pre-speci ated techniques involving liquid chromatog-
           raphy (LC)  and thin  layer chromatography (TLC) to  isolate specific
           PAHs,  particularly B[a]P  (8).  As with fluorescence  spectroscopy, the
           individual  spectra for various PAHs are  unique, although  portions
           of  spectra  for  different  compounds may be  the  same.  As with  flu-
           oresence techniques,  the  possibility  of  spectra overlap required
           complete separation  of sample  components to insure accurate  measure-
           ment of component  levels.  Hence, the use  of UV absorption coupled

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                              T013-2
     with pre-speciation involving LC and TLC and fluorescence spectro-
     scopy has declined and is now being replaced with the more sensitive
     high performance liquid chromatography (9)  with UV/fluorescence  detec-
     tion and highly sensitive and specific gas  chromatograph with  either
     flame ionization detector or coupled with mass spectroscopy (10-11).
1.3' The choice of GC and HPLC as the recommended procedures  for analysis
     of B[a]P and other PAHs are influenced by their sensitivity and
     selectivity, along with their ability to analyze complex samples.
     This method provides for both GC and HPLC approaches  to  the deter-
     mination of B[a]P and  other PAHs in the extracted sample.
1.4  The analytical  methodology is well  defined,  but the sampling pro-
     cedures  can reduce the validity of  the analytical  results.   Recent
     studies  (12-15) have indicated that non-volatile PAHs  (vapor pres-
     sure <10'8 mm Hg)  may  be trapped on the filter,  but post-collection
     volatilization problems may distribute the PAHs down  stream of the
     the filter to the  back-up  adsorbent.   A wide variety  of  adsorbents
     such as  Tenax GC,  XAD-2 resin and polyurethane  foam (PUF)  have been
     used to  sample  B[a]P and  other PAH  vapors.   All  adsorbents  have
     demonstrated  high  collection  efficiency for  B[a]P  in particular.
     In  general, XAD-2  resin has a  higher  collection  efficiency  (16-17)
     for volatile  PAHs  than  PUF, as well  as  a  higher  retention efficiency.
     However, PUF  cartridges  are easier  to  handle  in  the field and main-
     tain better flow characteristics during sampling.  Likewise, PUF
     has demonstrated its capability  in  sampling organochlorine  pesticides
     and  polychlorinated  biphenyls  (Compendium Methods T04 and TO 10 re-
     spectively),  and polychlorinated dibenzo-p-dioxins (Compendium
     Method T09).  However,  PUF has demonstrated a lower recovery effi-
     ciency and storage capability  for naphthalene and B[a]P, respectively,
     than XAD-2.   There have been  no significant losses of PAHs, up to
     30  days of storage at 0°C, using XAD-2.  It also appears that XAD-2
     resin has  a higher collection efficiency for volatile PAHs than
     PUF, as well  as a higher retention  efficiency for both volatile and
     reactive PAHs.  Consequently, while the literature cites weaknesses
     and  strengths of using either XAD-2 or PUF,  this method covers both
     the  utilization of XAD-2 and PUF as the adsorbent to address post-
     collection volatilization problems associated with B[a]P and other
     reactive PAHs.

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                                  T013-3
     1.5   This  method  covers  the determination of B[a]P specificially by
          both  GC  and  HPLC  and  enables the qualitative and quantitative
          analysis of  the other PAHs.  They are:
          Acenaphthene                       Benzo(k)fluoranthene
          Acenaphthylene                     Chrysene
          Anthracene                         Dibenzo(a,h)anthracene
          Benzo(a)anthracene                  Fluoranthene
          Benzo(a)pyrene                     Fluorene
          Benzo(b)fluoranthene                Indeno(l,2,3-cd)pyrene
          Benzo(e)pyrene                     Naphthalene
          Benzo(g,h,i)perylene                Phenanthrene
                                             Pyrene
          The GC and HPLC methods  are  applicable to the determination of
          PAHs  compounds involving two-member rings or higher.  Nitro-
          PAHs  have not  been  fully evaluated using this procedure; therefore,
          they  are not included in this  method.  When either of the methods
          are used to  analyze unfamiliar samples for any or all of the com-
          pounds listed  above,  compound  identification should be supported
          by both  techniques.
     1.6   With  careful attention to  reagent purity and optimized analytical
          conditions,  the detection  limits  for GC and HPLC methods range  from
          1 ng  to  10 pg  which represents detection of B[a]P and other PAHs
          in filtered  air at  levels  below 100 pg/m3.  To obtain this detection
          limit, at least 100 m3 of  air  must be  sampled.
2.  Applicable  Documents
     2.1   ASTM  Standards
          2.1.1  Method  D1356 - Definitions of Terms Relating to Atmospheric
                 Sampling and Analysis.
          2.1.2  Method  E260  -  Recommended  Practice  for General Gas
                 Chromatography Procedures.
          2.1.3  Method  E355  -  Practice  for Gas  Chromatography Terms and
                 Relationships.
          2.1.4  Method  E682  -  Practice  for Liquid Chromatography Terms and
                 Relationships.
          2.1.5  Method  D-1605-60  -  Standard Recommended Practices for Sampling
                 Atmospheres  for Analysis of Gases and Vapors.
      2.2  Other Documents
          2.2.1  Existing Procedures (18-25)
          2.2.2  Ambient Air  Studies (26-28)

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                                  T013-4
          2.2.3  U.S. EPA Technical  Assistance Document (29-32)
          2'2*4  General  Metal  Works Operating Procedures for Model  PS-1
                 Sampler, General  Metal  Works, Inc.,  Village of  Cleves, Ohio.
3.  Summary of Method
     3.1  Filters and adsorbent cartridges  (containing  XAD-2 or  PUF)  are
          cleaned in  solvents and  vacuum-dried.  The  filters and adsorbent
          cartridges  are  stored in screw-capped  jars  wrapped in  aluminum
          foil  (or  otherwise protected  from  light)  before  careful installa-
          tion  on a modified high  volume  sampler.
     3.2  Approximately 325 m3  of  ambient air  is drawn through the filter
          and adsorbent cartridge  using a calibrated  General  Metal Works
          Model PS-1  Sampler, or equivalent  (breakthrough has not shown
          to be a problem with  sampling volumes of 325 m3).
     3.3   The amount  of air sampled through the filter and adsorbent car-
          tridge  is recorded, and the filter and cartridge are placed in
          an appropriately labeled container and shipped along with blank
          filter  and adsorbent  cartridges to the analytical  laboratory
          for analysis.
    3.4  The filters and adsorbent cartridge are extracted by Soxhlet
          extraction with appropriate solvent.   The extract is concentrated
         by Kuderna-Danish (K-D) evaporator, followed by silica  gel  clean-up
         using column chromatography to remove potential interferences prior
         to analysis.
    3.5  The eluent is further  concentrated  by K-D evaporator, then  analyzed
         by either gas chromatograhy equipped  with FI or MS detection or  high
         performance  liquid  chromatography  (HPLC). The analytical system is
         verified to  be  operating  properly and calibrated with five  concen-
         tration  calibration  solutions,  each analyzed in triplicate.
    3.6  A preliminary analysis of the  sample  extract is performed to check
         the system performance and  to  ensure  that the  samples are within
         the calibration  range  of  the instrument.   If necessary, recalibrate
         the instrument,  adjust the  amount of  the  sample injected, adjust
         the calibration  solution  concentration, and  adjust  the  data  proces-
         sing system  to  reflect observed  retention times,  etc.
    3.7   The samples  and  the blanks  are analyzed and  used  (along with the
         amount of  air sampled)  to calculated  the  concentratuon  of B[a]P in
         ambient  air.

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                                   T013-5
     3.8  Other PAHs can be determined  both  qualitatively and quantitatively
          through optimization of the GC or  HPLC  procedures.
4.  Significance
     4.1  Several  documents have been published which describe  sampling and
          analytical approaches for benzo[a]pyrene  and  other PAHs,-as  out-
          lined in Section 2.2.  The attractive features of these methods
          have been combined in this procedure.   This method has been
          validated in the laboratory;  however, one must use caution when
          employing it for specific applications.
     4.2  The relatively low level  of B[a]P  and other PAHs  in the environ-  ,
          ment requires use of high volume (^.7  cfm) sampling  techniques
          to acquire sufficient sample  for analysis.  However,  the  volatility
          of certain PAHs prevents efficient collection on  filter media
          alone.  Consequently, this method  utilizes both  a filter  and a
          backup adsorbent cartridge which provide  for  efficient collection
          of most PAHs.
5.  Definitions
     Definitions used in this document  and in any user-prepared standard
operating procedures (SOPs) should be consistent  with ASTM  Methods  D1356,
D1605-60, E260, and E255.  All abbreviations and  symbols  are defined with-
in this document at point of use.
     5.1  Sampling efficiency (SE) - ability of the sampling medium to trap
          vapors of interest.  %SE is the percentage  of the analyte of in-
          terest colleted and retained  by the sampling  medium  when  it  is
          introduced as a vapor in air  or nitrogen  into the air sampler and
          the sampler is operated under normal  conditions  for  a period of
          time equal to or greater than that required for  the  intended use.
     5.2  Retention time (RT) - time to elute a specific  chemical  from a
          chromatographic column.  For  a specific carrier  gas  flow rate,
          RT is measured from the time  the chemical is  injected into  the
          gas stream until it appears at the detector.
     5.3  High Performance Liquid Chromatography  -  an analytical  method
          based on separation of compounds of a liquid  mixture through a
          liquid chromatographic column and measuring the  separated com-
          ponents with a suitable detector.

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                             T013-6
5.4  Gradient elution - defined as increasing the strength of the
     mobile phase during a chromatographic analysis.  The net effect
     of gradient elution is to shorten the retention time of compounds
     strongly retained on the analytical  column.  Gradient elution may
     be stepwise on continuous.
5.5  Method detection limit (MDL) - the minimum concentration of a sub-
     stance that can be measured and reported with confidence and that
     the value is above zero.
5.6  Kuderna-Danish apparatus - the Kuderna-Danish (KD)  appartus is a
     system for concentrating materials dissolved in volatile solvents.
5.7  Reverse phase liquid chromatography  - reverse phase liquid chro-
     matography involves a non-polar absorbent (C-18.0DS) coupled with
     a polar solvent to separate non-polar compounds.
5.8  Guard column - guard columns in HPLC are usually  short ( 5cm)
     columns attached after the injection port and before the analytial
     column to prevent particles and strongly retained compounds from
     accumulating on the analytical  column.  The guard column should
     always be the same stationary phase  as the analytical  column and
     is used to extend the life of the analytical  column.
5.9  MS-SIM - the GC is coupled to a select ion mode (SIM)  detector
     where the instrument is programmed to acquire data for only the
     target compounds and to disregard all  others.  This is performed
     using SIM coupled to retention time  discriminators.  The SIM
     analysis procedure provides quantitative results.
5.10 Sublimation - Sublimation is the direct passage of  a substance
     from the solid state to the gaseous  state and back  into the solid
     form without at any time appearing in the liquid  state.  Also
     applied to the conversion of solid to vapor without the later
     return to solid state, and to a conversion directly from the
     vapor phase to the solid state.
5.11 Surrogate standard - A surrogate standard is a chemically inert
     compound (not expected to occur in the environmental sample)
     which is added to each sample,  blank and matrix spiked sample
     before extraction and analysis. The  recovery of the surrogate
     standard is used to monitor unusual  matrix effects, gross sample
     processing errors, etc.  Surrogate recovery is evaluated for
     acceptance by determining whether the measured concentration
     falls within acceptable limits.

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                                   T013-7

    5.12  Retention time window -  Retention  time window is determined for
          each analyte of interest and  is  the time  from injection  to elution
          of a specific chemical from a  chromatographic column.  The window
          is determined by three injections  of  a single component  standard over
          a 72-hr period as plus or minus  three times  the standard  deviation
          of the absolute retention time for that  analyte.
6.  Interferences
     6.1  Method interferences may be  caused by contaminants  in  solvents,
          reagents, glassware, and other sample processing hardware that
          result in discrete artifacts  and/or elevated baselines  in the
          detector profiles.  All  of these materials must be  routinely
          demonstrated to be free  from  interferences under the conditions
          of the analysis by running laboratory reagent blanks.
          6.1.1  Glassware must be scrupulously cleaned (33).  Clean all
                 glassware as soon as  possible  after use by  rinsing with
                 the last solvent  used  in it.  This should be  followed  by
                 detergent washing with hot  water,  and rinsing with tap
                 water and reagent water.   It should then be  drained dry,
                 solvent rinsed with acetone and spectrographic  grade
                 hexane.  After drying  and rinsing, glassware should be
                 sealed and stored in  a clean environment to  prevent any
                 accumulation of dust  or other  contaminants.   Glassware
                 should be stored  inverted or capped with aluminum foil.
          6.1.2  The use of high purity water,  reagents and  solvents helps to
                 minimize interference problems.   Purification  of solvents
                 by distillation in all-glass systems  may be  required.
          6.1.3  Matrix interferences  may be caused by contaminants that
                 are coextracted from  the sample.   Additional  clean-up  by
                 column chromatography may be required (see  Section 12.4).
     6.2  The extent of interferences  that may  be  encountered using liquid
          chromatographic techniques has not been  fully assessed.   Although
          GC and HPLC conditions described allow  for unique  resolution
          of the specific PAH compounds covered by this method,  other PAH
          compounds may interfere.  The use  of  column  chromatography  for
          sample clean-up prior to GC  or HPLC analysis will  eliminate most

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                                   T013-8

          of these interferences.  The analytical system must, however, be
          routinely demonstrated to be free of internal  contaminants such
          as contaminated solvents, glassware, or other reagents which may
          lead to method interferences.  A laboratory reagent blank is run
          for each batch of reagents used to determine if reagents are
          contaminant-free.
     6.3  Although HPLC separations have been improved by recent advances
          in column technology and instrumentation, problems may occur with
          baseline noise, baseline drift, peak resolution and changes in
          sensitivity.  Problems affecting overall  system performance can
          arise (34).   The user is encouraged to develop a standard operating
          procedure (SOP) manual specific for his laboratory to minimize
          problems affecting overall  system performance.
     6.4  Concern during sample transport and analysis is mentioned.   Heat,
          ozone,  N02  and ultraviolet  (UV) light may cause sample degradation.
          These problems should be addressed  as part of  the  user prepared
          standard operating procedure manual.  Where possible, incandescent
          or UV-shield fluorescent lighting should  be used during  analysis.
7.  Safety
     7.1  The toxicity or carcinogenicity of  each reagent  used  in  this
          method  has not been  precisely defined;  however,  each  chemical
          compound should be treated  as a potential  health hazard.  From
          this  viewpoint, exposure to  these chemicals must be  reduced to
          the lowest possible  level by whatever means available.   The
          laboratory is responsible for maintaining a current  awareness
          file  of  Occupational  Safety  and Health  Administration (OSHA)
          regulations  regarding the safe  handling of the  chemicals  speci-
          fied  in  this method.   A  reference file  of  material  data  handling
          sheets  should also be made available to all  personnel  involved  in
          the chemical  analysis.   Additional  references  to laboratory
          safety  are available  and have been  identified  for  the analyst
          (35-37).
     7.2  Benzo[a]pyrene has been  tentatively  classified as  a known or
          suspected, human or mammalian carcinogen.   Many  of the other PAHs
          have  been classified  as  carcinogens.  Care must  be exercised when

-------
                                  T013-9
         working with these substances.  This method does not purport to
         address all of the safety problems associated with its use.  It
         is  the  responsibility of whoever uses this method to consult and
         establish  appropriate safety and health practices and determine
         the applicability of regulatory limitations prior to use.  The
         user should be thoroughly familiar with the chemical and physical
         properties of targeted substances (Table 1.0 and Figure 1.0).
     7.3  Treat all  selective  polynuclear aromatic hydrocarbons as carcinogens.
         Neat compounds should be weighed in  a glove box.  Spent samples  and
         unused standards  are toxic waste and should be  disposed according to
         regulations.  Regularly check counter tops and  equipment with  "black
         light" for fluorescence as an indicator of contamination.
     7.4  Because the  sampling configuration  (filter and  backup adsorbent) has
         demonstrated  greater than 95% collection efficiency  for targeted PAHs,
         no field recovery evaluation will occur as part of  this procedure.

8.  Apparatus
     8.1   Sample Collection
         8.1.1  General  Metal  Works  (GMW)  Model PS-1  Sampler, or equi-
                 valent [General  Metal  Works,  Inc.,  145  South Miami  Ave.,
                 Village  of Cleves, Ohio,  45002,  (800-543-7412)].
          8.1.2  At least  two Model  PS-1  sample  cartridges and filters
                 assembled for PS-1  sampler.
          8.1.3  GMW Model PS-1  calibrator and associated equipment  -
                 General  Metal  Works,  Inc., Model GMW-40, 145 South  Miami
                 Ave., Village of Cleves, Ohio,  45002, (800-543-7412).
          8.1.4  Ice chest - to store samples at 0°C after collection.
          8.1.5  Data sheets for each sample for recording the location and
                 sample time, duration of sample,  starting time, and volume
                 of air sampled.
          8.1.6  Airtight, labeled screw-capped container sample cartridges
                 (wide mouth, preferrably glass with Teflon seal  or other non-
                 contaminating seals) to hold filter and adsorbent cartridge
                 during transport to analytical  laboratory.
          8.1.7  Portable Tripod Sampler (optional) - user prepared (38).
     8.2  Sample Clean-up and Concentration
          8.2.1  Soxhlet  extractors capable of extracting GMW Model  PS-1
                 filter and adsorbent cartridges (2.3" x  5"  length), 500  ml
                 flask, and condenser.

-------
                          T013-10
  8.2.2  Pyrex glass tube furnace system for activating  silica  gel
         at 180°C under purified nitrogen gas  purge  for  an  hour,
         with capability of raising  temperature gradually.
  8.2.3  Glass vial, 40 ml.
  8.2.4  Erlenmeyer flask,  50  ml - best  source.  [Note:  Reuse of
         glassware  should be minimized to  avoid the  risk of cross-
         contamination.  All glassware that  is used, especially glass-
         ware  that  is reused,  must be scrupulously cleaned as soon
         as  possible  after use.  Rinse glassware with the last solvent
         used  in  it  and then with high-purity acetone and hexane.
         Wash with  hot water containing detergent.  Rinse with copious
         amount of tap water and several  portions  of distilled water.
         Drain, dry, and heat  a muffle furnace at  400°C for 2 to 4
         hours.  Volumetric glassware must not be  heated in a muffle
         furnace;  rather, it should be rinsed with high-purity acetone
        and hexane.  After the glassware is dry and  cool,  rinse it
        with hexane, and store it inverted or capped with  solvent-
        rinsed aluminum foil  in a clean  environment.]
 8.2.5  Polyester gloves for  handling  cartridges  and filters.
 8.2.6  Minivials - 2 ml, borosilicate glass,  with conical  reservoir
        and  screw caps  lines with Teflon-faced silicone  disks,  and
        a vial  holder.
 8.2.7  Stainless steel  Teflon® coated spatulas and  spoons.
 8.2.8  Kuderna-Danish  (KD) apparatus - 500  ml evaporation flask
        (Kontes K-570001-500 or equivalent), 10 ml graduated con-
        centrator tubes  (Knotes  K-570050-1025 or equivalent) with
        ground-glass  stoppers,  and 3-ball macro Snyder Column (Kontes
        K-5700010500, K-50300-0121, and K-569001-219, or equivalent).
 8.2.9   Adsorption  columns for  column chromatography -  1-cm x 10-cm
        with stands.
 8.2.10 Glove box for working  with extremely toxic standards and
        reagents with explosion-proof hood for venting  fumes from
        solvents,  reagents,  etc.
8.2.11 Vacuum Oven - Vacuum drying oven  system capable of  maintaining
       a vacuum at 240  torr (flushed with nitrogen)  overnight.
8.2.12 Concentrator tubes  and  a nitrogen evaporation apparatus
       with variable flow rate - best  source.

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                             T013-11

     8.2.13 Laboratory refrigerator with  chambers operating at 0°C and 4°C.
     8.2.14 Boiling  chips -  solvent extracted,  10/40 mesh silicon car-
            bide or  equivalent.
     8.2.15 Water bath -  heated,  with  concentric  ring cover, capable
            of temperature control  (+_  5°C).
     8.2.16 Vortex evaporator (optional).
8.3  Sample Analysis
     8.3.1  Gas Chromatography with Flame lonization Detection  (FID).
            8.3.1.1   Gas  Chromatography:   Analytical system complete
                     with gas Chromatography  suitable for on-column
                     injections  and  all  required  accessories, including
                     detectors,  column supplies,  recorder, gases, and
                     syringes.  A data system for measuring  peak areas
                     and/or peak  heights  is  recommended.
            8.3.1.2  Packed Column:   1.8-m x  2-mm I.D.  glass column
                     packed with 3%  OV-17 on  Chromosorb W-AW-DMCS
                     (100/120 mesh)  or equivalent (Supelco Inc.,
                     Supelco Park, Bellefonte,  Pa.  Supelco SPB-5).
            8.3.1.3  Capillary Column:  30-m  x 0.25-mm  ID  fused silica
                     column coated with 0.25  u thickness 5%  phenyl,
                     90% methyl  siloxane (Supelco Inc., Supelco Park,
                     Bellefonte, Pa.).
            8.3.1.4  Detector:  Flame  lonization (FI)
     8.3.2  Gas Chromatograph with Mass Spectroscopy  Detection  Coupled
            with Data Processing System (GC/MS/DS).
            8.3.2.1  The GC must be equipped for temperature programming,
                     and all  required  accessories must  be  available,  in-
                     cluding  syringes, gases, and a capillary  column.   The
                     GC  injection port must be designed for  capillary
                     columns.  The use of splitless injection  techniques
                     is  recommended.   On-column injection techniques  can  be
                     used but they may severely reduce  column  lifetime  for
                     nonchemically bonded columns.  In  this  protocol, a 1-3
                     uL  injection volume is used consistently.   With  some
                     GC  injection ports, however, 1 uL injections  may pro-
                     duce some improvement in  precision and  chromatographic

-------
                  T013-12
          separation.  A 1 uL injection volume may be used if
          adequate sensitivity and precision can be achieved.
          [NOTE:  If 1 uL is used as the injection volume, the
          injection volumes for all  extracts,  blanks, calibra-
          tion solutions and performance check samples must be
          1 uL.]
 8.3.2.2  Gas Chromatograph-Mass Spectrometer  Interface.   The
          gas chromatograph is  usually coupled directly to the
          mass spectrometer source.   The interface may include
          a diverter valve for  shunting the  column effluent and
          isolating  the mass spectrometer source.   All  compo-
          nents  of the interface should be glass or glass-lined
          stainless  steel.   The  interface components  should
          be compatible with 320°C temperatures.   Cold spots
          and/or active surfaces  (adsorption sites) in  the
          GC/MS  interface  can cause  peak  tailing and  peak
          broadening.   It  is  recommended  that  the  GC  column
          be fitted  directly  into the MS  source.   Graphic
          ferrules should  be  avoided in the GC injection area
          since  they may adsorb PAHs.   Vespel® or  equivalent
          ferrules are  recommended.
8.3.2.3   Mass Spectrometer.  The static  resolution of the  in-
          strument must be maintained at  a minimum of 10,000
          (10 percent valley).  The mass  spectrometer should
          be operated in the  selected ion mode (SIM) with  a total
          cycle time (including voltage reset time) of one
          second or less (Section 14.2).
8.3.2.4  Mass spectrometer:  Capable of scanning from 35  to
         500 amu every 1 sec or less, using  70 volts
          (nominal) electron energy in the electron impact
          ionization mode.  The mass  spectrometer must be
         capable of producing a mass spectrum for decafluoro-
         triphenylphosphine (DFTPP)  which meets all of the
         criteria (Section 14.5.1).
8.3.2.5  Data System.   A dedicated computer  data system
         is employed to control  the  rapid multiple ion
         monitoring  process and to acquire the data.
         Quantification data (peak areas or  peak  heights)
         and multi-ion detector (MID)  traces  (displays
         of intensities of each  m/z  being monitored

-------
                       T013-13
               as a function of time) must be acquired during the
               analyses.  Quantifications may be reported based
               upon computer-generated peak areas or upon measured
               peak heights (chart recording).  The detector zero
               setting must allow peak-to-peak measurement of the
               noise on the baseline.
       8.3.2.6  GC Column.  A fused silica column (50-m x 0.25-mm
               I.D.) HP Ultra #2 crosslinked 5% phenyl methylsili-
               cone, 0.25 urn film thickness (Hewlett-Packard Co.,
               Crystal Lake, IL) is  utilized to separate individual
               PAHs.  Other columns  may be used for determination
               of PAHs.  Minimum acceptance criteria must be deter-
               mined as per Section  14.2.  At the beginning of each
               12-hour period (after mass resolution has been demon-
               strated) during  which sample extracts or concentra-
               tion calibration solutions will  be analyzed, column
               operating  conditions  must be attained for the required
               separation on the column to be used for samples.
       8.3.2.7  Balance -  Mettler balance or equivalent.
       8.3.2.8  All  required  syringes,  gases, and other pertinent
               supplies to  operate the GC/MS  system.
       8.3.2.9  Pipettes,  micropipettes, syringes, burets, etc., to
               make calibration and  spiking solutions, dilute  samples
                if  necessary, etc., including  syringes  for accurately
               measuring  volumes such  as 25 uL  and 100 uL.
8.3.3  High Performance  Liquid Chromatography  (HPLC)  System.
       8.3.3.1  Gradient  HPLC system  -  Consisting of  acetonitrile  and
               water  phase  reservoirs; mixing  chamber; a  high  pres-
                sure pump;  an  injection valve  (automatic  sampler
               with an  optional 25  uL  loop  injector);  a  Vydac  C-18
                bonded  phase  reverse  phase  (RP)  column,  (The  Separa-
               tions  Group,  P.O.  Box 867,  Hesperia,  CA 92345)  or
                equivalent (25-cm  x  4.6-mm  ID);  a variable wavelength
                UV/Fluorescence  detector  and  a data  system or strip
                chart  recorder.  A  Spectra  Physics 8100 liquid  chromat-
                ograph multi-microprocessor controlled, with  ternary
                gradient  pumping system,  constant  flow, autosampler
                injector (10 uL  injection  loop), and  column  oven
                (optional).

-------
                                   T013-14

                  8.3.3.2  Guard  column  -  5-cm  guard  column  pack with Vydac
                           reverse  phase C-18 material.
                  8.3.3.3  Reverse  phase analytical column - Vydac or equivalent,
                           C-18 bonded phase RP column (The Separation Group,
                           P.O. Box 867, Hesperia, Ca., 92345), 4.6-mm x 25-cm,
                           5-micron particle diameter.
                  8.3.3.4   LS-4 fluorescence spectrometer, Perkin Elmer, sepa-
                           ate excitation and emission, monochromator positioned
                           by separate microprocessor-controlled flow cell  and
                           wavelength programming ability (optional).
                 8.3.3.5   Ultraviolet/visible detector,  Spectra Physics 8440,
                           deuterium Lamp,  capable of  programmable wavelengths
                           (optional).
                 8.3.3.6  Dual  channel  Spectra  Physics 4200  Computing  Integra-
                          tor,  measures  peak areas  and retention times  from
                          recorded  chromatographs.  IBM  PC XT  will Spectra
                          Physics Labnet system for data  collection  and  storage
                          (optional).
9.  Reagents and Materials
     9.1  Sample Collection
          9.1.1   Acid-washed quartz fiber  filter  - 105 mm micro quartz fiber
                 binderless filter  (General Metal Works,  Inc., Cat.  No. GMW
                 QMA-4,  145 South Miami  Ave., Village  of Cleves, Ohio,
                 45002 [800-543-7412] or Supeico  Inc., Cat. No. 1-62,
                 Supeico  Park, Bellefonte, PA, 16823-0048).
          9.1.2   Polyurethane foam (PUT) - 3 inch thick sheet stock,
                 polyether  type (density 0.022 g/cm3)  used in furniture
                 upholstering (General Metal  Works, Inc., Cat.  No.  PS-1-16,
                 145 South Miami Ave., Village of Cleves, Ohio, 45002 [800-
                543-7412] or Supeico Inc., Cat. No.  1-63, Supeico Park,
                Bellefonte, PA, 16823-0048).
         9.1.3  XAD-2 resin -  Supeico Inc.,  Cat.  No.  2-02-79,  Supeico
                Park, Bellefonte, PA,  16823-0048.
         9.1.4  Hexane-rinsed  aluminum foil  - best  source.
         9.1.5  Hexane-reagent  grade,  best source.

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                             T013-15

9.2  Sample Clean-up and Concentration
     9.2.1  Soxhlet Extraction
            9.2.1.1  Methylene chloride  -  chromatographic  grade,
                     glass-distilled,  best source.
            9.2.1.2  Sodium sulfate,  anhydrous -  (ACS)  granular
                     anhydrous (purified by washing  with methylene
                     chloride followed by heating at 400°C for 4  hrs
                     in a shallow tray).
            9.2.1.3  Boiling chips -  solvent extracted, approximately
                     10/40 mesh (silicon carbide  or equivalent).
            9.2.1.4  Nitrogen - high  purity grade, best source.
            9.2.1.5  Ether - chromatographic grade, glass-distilled,
                     best source.
            9.2.1.6  Hexane - chromatographic grade, glass-distilled,
                     best source.
            9.2.1.7  Dibromobiphenyl  - chromatographic grade, best source,
                     Used for internal standard.
            9.2.1.8  Decafluorobiphenyl - chromatographic grade, best
                     source.  Used for  internal standard.
      9.2.2  Solvent  Exchange
            9.2.2.1  Cyclohexane  - chromatographic  grade, glass-
                     distilled, best  source.
      9.2.3  Column Clean-up
                                    Method  610
            9.2.3.1  Silica  gel - high  purity  grade, type 60, 70-230
                     mesh;  extracted  in a Soxhlet  apparatus  with
                     methylene  chloride for 6  hours (minimum of 3
                     cycles  per hour) and activated by heating in a
                     foil-covered glass container for  24  hours at 130°C.
             9.2.3.2 Sodium sulfate,  anhydrous - (ACS) granular
                     anhydrous  (See  Section 9.2.1.2).
             9.2.3.3 Pentane -  chromatographic grade,  glass-distilled,
                     best source.

-------
                              T013-16

                                Lobar Prepacked Column
            9.2.3.4  Silica gel lobar prepacked column - E. Merck,
                     Darmstadt, Germany [Size A(240-10) Lichroprep Si
                     (40-63 urn)].
            9.2.3.5  Precolumn containing sodium sulfate - American
                     Chemical Society (ACS) granular anhydrous (purified
                     by washing with methylene chloride followed by
                     heating at 400°C for 4 hours in a shallow tray).
            9.2.3.6  Hexane - chromatographic grade, glass-distilled,
                     best source.
            9.2.3.7  Methylene chloride  - chromatographic  grade, glass-
                     distilled, best source
            9.2.3.8  Methanol  - chromatographic  grade, glass-distilled,
                     best source.
9.3  Sample Analysis
     9.3.1  Gas Chromatography Detection
            9.3.1.1  Gas  cylinders  of  hydrogen and helium  - ultra  high
                     purity,  best  source.
            9.3.1.2  Combustion air -  ultra high  purity, best  source.
            9.3.1.3  Zero  air  -  Zero air may be obtained from  a  cylinder
                     or zero-grade  compressed air scrubbed with  Drierite®
                     or silica gel  and 5A molecular  sieve or activated
                     charcoal,  or by catalytic cleanup of ambient air.
                     All zero  air should be  passed through a liquid
                     argon cold trap for final cleanup.
            9.3.1.4   Chromatographic-grade  stainless steel tubing
                     and stainless  steel  plumbing fittings - for
                     interconnections.  [Alltech Applied Science,
                     2051 Waukegan  Road, Deerfield,  IL, 60015, (312)
                     948-8600].  [Note:  Al1 such materials in contact
                     with the  sample, analyte, or support gases prior
                     to analysis should be stainless steel  or other
                     inert metal.  Do not use plastic or Teflon®
                     tubing or fittings.]

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                                  T013-17

                 9.3.1.5  Native and isotopically labeled  PAHs isomers  for
                          calibration and spiking standards-CCambridge
                          Isotopes, 20 Commerce Way,  Woburn, MA,  01801  (617-
                          547-1818)].  Suggested isotopically labeled PAH
                          isomers are:
                            o  perylene - d\2
                            o  chrysene - d^2
                            o  acenaphthene -
                            o  naphthalene -
                            o  phenanthrene -
                 9.3.1.6  Decafluorotriphenylphosphine (DFTPP) - best source,
                          used for tuning GC/MS.
           9.3.2  High Performance Liquid Chromatography Detection
                 9.3.2.1  Acetonitrile - chromatographic grade, glass-
                          distilled,  best source.
                 9.3.2.2  Boiling chips  - solvent extracted, approximatley
                          10/40 mesh  (silicon  carbide or equivalent).
                 9.3.2.3  Water - HPLC Grade.  Water must not have an
                          interference that  is observed at  the minimum
                          detectable  limit  (MDL)  of each parameter of interest.
                 9.3.2.4  Decafluorobiphenyl - HPLC grade,  best source
                          (used for  internal standard).
10.  Preparation  of Sample Filter  and  Adsorbent
     10.1  Sampling Head Configuration
           10.1.1  The  sampling  head  (Figure  2) consist of a filter holder
                   compartment  followed by a  glass cartridge for retaining
                   the  adsorbent.
           10.1.2  Before  field  use,  both the filter and adsorbent must be
                   cleaned to  <10  ng/apparatus  of B[a]P or other PAHs.
     10.2  Glass  Fiber  Filter  Preparation
           10.2.1  The  glass fiber filters are  baked at 600°C for five  hours
                   before  use.   To insure acceptable filters, they are  ex-
                   tracted with  methylene chloride in  a  Soxhlet  apparatus, sim-
                   ilar to the cleaning  of the  XAD-2  resin  (see  Section 10.3).

-------
                              T013-18

      10.2.2  The extract is concentrated and analyzed by either GC or
              HPLC.  A filter blank of <10 ng/filter of B[a]P or other
              PAHs is considered acceptable for field use.
10.3.  XAD-2 Adsorbent Preparation
      10.3.1  For initial cleanup of the XAD-2, a batch of XAD-2 (approxi-
              mately 60 grams)  is placed in a Soxhlet apparatus  [see Fig-
              ure 3(a)] and  extracted with methylene chloride for 16
              hours at approximately 4 cycles per hour.
      10.3.2  At the end of  the initial  Soxhlet extraction, the  spent
              methylene chloride is discarded and replaced with  fresh
              reagent.  The  XAD-2 resin is once again extracted  for 16
              hours at approximately 4 cycles per hour.
      10.3.3  The XAD-2 resin is removed from the Soxhlet apparatus,
              places in a vacuum oven connected to an ultra-purge nitrogen
              gas stream and dries at room temperature for approximately
              2-4 hours (until  no solvent odor is detected).
      10.3.4  A nickel  screen (mesh size 200/200) is fitted to the bottom
              of a hexane-rinsed glass cartridge to retain the XAD-2 resin.
      10.3.5  The Soxhlet extracted/vacuum dried XAD-2 resin is  placed into
              the sampling cartridge (using polyester gloves) to a depth
              of approximately  2 inches.  This should require approxi-
              mately 55 grams of adsorbent.
      10.3.6  The glass module  containing the XAD-2 adsorbent is wrapped
              with hexane-rinsed aluminum foil, placed in a labeled
              container and  tightly sealed with Teflon® tape.
      10.3.7  At least one assemble cartridge from each batch must be
              analyzed, as a laboratory blank, using the procedures
              described in Section 13, before the batch is considered
              acceptable for field use.   A blank of <10 ng/cartridge of
              B[a]P on other PNA's is considered acceptable.
10.4  PDF Sampling Cartridge Preparation
      10.4.1  The PUF adsorbent is a polyether-type polyurethane foam
              (density No. 3014 or 0.0225 g/cm3) used for furniture up-
              holstery.

-------
                                 T013-19

         10.4.2  The PUF inserts are 6.0-cm diameter  cylindrical plugs cut
                 from 3-inch sheet stock  and should fit, with  slight
                 compression, in the glass cartridge, supported  by the
                 wire screen (see Figure  1).  During  cutting,  the die is
                 rotated at high speed (e.g., in a drill press)  and
                 continuously lubricated  with water.
         10.4.3  For initial cleanup, the PUF plug is placed  in  a Soxhlet
                 apparatus [see Figure 3(a)] and extracted with  acetone
                 for 14-24 hours at approximately 4 cycles per hour.
                 [Note:  When cartridges  are reused,  5% diethyl  ether  in
                 n-hexane can be used as the cleanup solvent.]
         10.4.4  The extracted PUF is placed in a vacuum oven connected to
                 a water aspirator and dried at room temperature for
                 approximately 2-4 hours (until no solvent odor is  detected).
         10.4.5  The PUF is  placed into the glass sampling cartridge using
                 polyester  gloves.  The module is wrapped with hexane-
                 rinsed aluminum foil, placed in a labeled container,  and
                 tightly sealed.
         10.4.6  At  least one assembled cartridge from each batch must be
                 analyzed,  as a  laboratory  blank, using the procedures
                 described  in Section 13,  before the  batch is considered
                 acceptable for  field use.   A  blank  level of  <10 ng/plug
                 for single compounds is considered  to be acceptable.

11.  Sample Collection
     11.1  Description  of  Sampling  Apparatus
           11.1.1  The  entire sampling system can  be  a modification of a
                   traditional high volume  sampler  (see Figure 4) or a portable
                   sampler (see  Figure 5).   A unit  specifically  designed for
                   this method is commercially available  (Model  PS-1 -
                   General  Metal  Works,  Inc., Village of Cleves, Ohio).
           11.1.2  The sampling  module consists of a  glass sampling  cartridge
                   and an air-tight metal  cartridge holder, as outlined in
                   Section 10.1.  The adsorbent (XAD-2 or  PUF) is retained
                   in the glass  sampling  cartridge.

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                             T013-20
11.2  Calibration of Sampling System
      Each sampler is to  be  calibrated:  1) when  new; 2) after major
      repairs or maintenance;  3)  whenever any  audit  point deviates
      from the calibration curve  by more than  7%; 4) when a different
      sample collection media,  other  than that which the sampler was
      originally calibrated  to, will  be  used for sampling; or 5) at the
      frequency specified in the  user Standard Operating Procedure (SOP)
      manual  in which the samplers are utilized.
      11.2.1  Calibration of Flow Rate Transfer  Standard
              Calibration of the  modified high volume air sampler in
              the field is performed  using a calibrated orifice flow
              rate transfer  standard.  The flow  rate transfer standard
              must be certified in the laboratory against a positive
              displacement rootsmeter (see Figure 6).  Once certified,
              the recertification is  performed rather infrequently if
              the orifice is protected from damage.  Recertification
              of the orifice flow rate transfer  standard is performed
              once per year  utilizing  a  set of five  (5) multihole re-
              sistance plates.  [Note: The 5 multihole resistance
              plates are  used to  change  the flow through the orifice so
              that several points can  be obtained for the orifice cali-
              bration curve.]
              11.2.1.1  Record the room temperature  (tj in °C) and barome-
                       tric pressure  (P& in mm  Hg) on Orifice Calibra-
                       tion Data Sheet  (see Figure 7).  Calculate the
                       room temperature in °K (absolute temperature)
                       and  record on  Orifice  Calibration Data Sheet.
                             ti in K  = 273° +  ti in °C
              11.2.1.2  Set  up laboratory orifice calibration equipment
                       as illustrated in Figure 6.  Check the oil level
                       of the  rootsmeter prior to starting.  There are
                       three oil level  indicators, one at the clear
                       plastic end,  and two sight glasses, one at each
                       end  of the measuring chamber.

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               T013-21

11.2.1.3  Check for leaks  by  clamping  both manometer lines
          blocking the  orifice  with  cellophane tape, turning
          on the high volume  motor,  and  noting any change
          in the rootsmeter's reading.   If the rootsmeter's
          reading changes, then there  is a leak  in the  sys-
          tem or in the tape.  Eliminate the  leak before
          proceeding.  If  the rootsmeter's reading remains
          constant, turn off  the hi-vol  motor, remove the
          cellophane tape, and  unclamp both manometer lines.
11.2.1.4  Install the 5-hole  resistance  plate between the
          orifice and the  filter adapter.
11.2.1.5  Turn manometer tubing connectors one turn counter-
          clockwise. Make sure all  connectors are open.
11.2.1.6  Adjust both manometer midpoints by  sliding their
          movable scales until  the zero  point corresponds
          with the bottom of  the meniscus.   Gently shake
          or tap to remove any  air bubbles  and/or  liquid
          remaining on  tubing connectors.  (If additional
          liquid is required  for the water manometer,
          remove tubing connector and add clean  water).
11.2.1.7  Turn on the hi-vol  motor and let  it run  for
          five minutes  to set the motor  brushes.
11.2.1.8  Record both manometer readings-orifice water  mano-
          meter  (AH) and rootsmeter mercury  manometer  (AP).
          [Note:  AH is the sum of the difference  from  zero
          (0) of the two column heights.]
11.2.1.9  Record the time, in minutes, required  to  pass a
          known  volume of air  (approximately 200-300  ft3 of
          air for each resistance plate) through the  roots-
          meter  by  using the rootsmeter's digital  volume dial
          and a  stopwatch.
11.2.1.10 Turn  off  the high volume motor.
11.2.1.11 Replace the  5-hole resistance plate with  the  7-
          hole  resistance plate.
11.2.1.12 Repeat Sections 11.2.1.3 through 11.2.1.10.

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               T013-22

11.2.1.13 Repeat for each resistance plate.   Note  results
          on Orifice Calibration Data Sheet  (see Figure  7).
          Only a minute is needed for warm-up of the motor.
          Be sure to tighten  the orifice  enough to  elimi-
          nate any leaks.  Also check the gaskets  for
          cracks.  [Note: The placement of the orifice
          prior to the rootsmeter causes  the  pressure at
          the inlet of the rootsmeter to  be  reduced below
          atmospheric conditions, thus causing the  measured
          volume to be incorrect.  The volume measured
          by the rootsmeter must be corrected.]
11.2.1.14 Correct the measured volumes with  the following
          formula and record  the standard volume on the
          Orifice Calibration Data Sheet:
                   Vstd  = Vm  Pi -AP   Tstd
                                 Pstd     T!
                                                o
           where:  Vg^  = standard volume (std m  ).
                   Vm    = actual volume  measured  by the
                           rootsmeter (m^).
                   P!    = barometric pressure during cali-
                           bration (mm Hg).
                   AP    = differential  pressure at inlet
                           to volume meter (mm Hg).
                   Pstd  = 760 mm Hg.
                   Tstd  = 298 K.
                   TI    = ambient temperature during cali-
                           bration (K).
11.2.1.15  Record standard volume on Orifice Calibration
           Data Sheet.
11.2.1.16  The standard flow rate as measured by the
           rootsmeter can now be calculated  using  the
           following formula:
                   Qstd  =   Vstd
                              9
           where:  Q$td  = standard volumetric flow rate,
                           std m3/min.
                    9  = elapsed time, min.

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                       T013-23
        11.2.1.17   Record  the  standard  flow  rates  to the  nearest
                   0.01 std  m3/min.
        11.2.1.18   Calculate and  record  \AH(Pi/Pstd)  (298/Ti)
                   value for each  standard flow rate.
        11.2.1.19   Plot each ^AH(Pi/Pstd) (298/T!) value  (y-axis)
                   versus  its  associated  standard  flow rate  (x-axis)
                   on arithmetic  graph  paper,  draw a line  of best
                   fit between  the individual  plotted  points and
                   calculate the  linear regression slope  (M)  and
                   intercept (b).
        11.2.1.20   Commercially available calibrator kits  are
                   available [General Metal  Works  Inc., Model
                   GMW-40, 145  South Miami Avenue, Village of
                   Cleves, Ohio,  45002  (1-800-543-7412)].
11.2.2  Calibration of The High Volume  Sampling System Utilizing
        Calibrated Multi-point  Flow Rate Transfer  Standard
        11.2.2.1   The airflow through  the sampling system can  be
                   monitored by a  venturi/magnehelic assembly,  as
                   illustrated  in  Figure 4 or  by a u-tube  assembly
                   connected to the high volume portable  design as
                   illustrated  in  Figure 5.  The field sampling sys-
                   tem must be  audited  every six months using a
                   flow rate transfer standard, as described in the
                   U.S. EPA High  Volume Sampling Method,  40 CFR 50,
                   Appendix B.  A single-point calibration must be
                   performed before and after  each sample  collec-
                   tion, using a  transfer standard calibrated as
                   described in Section 11.2.1.
        11.2.2.2   Prior to initial  multi-point calibration, a
                   "dummy" adsorbent cartridge and filter are
                   placed in the  sampling head and the sampling
                   motor is activated.   The  flow control  valve
                   is fully opened and  the voltage variator is
                   adjusted so  that a  sample flow  rate corresponding
                   to 110% of the desired flow rate  (typically
                   0.20 - 0.28  m3/min)  is indicated on the
                   Magnehelic gauge (based  on  the  previously
                   obtained multi-point calibration curve).  The

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              T013-24

           motor is allowed to warm up for 10 minutes  and
           then the flow control  valve is  adjusted to
           achieve the desired flow rate.   Turn  off the
           sampler.  The ambient  temperature  and baro-
           metric pressure should be recorded on the Field
           Calibration Data Sheet (Figure  9).
11.2.2.3   The flow rate transfer standard is placed on
           the sampling head, and a manometer is connected
           to the tap on the transfer standard using a
           length of tubing.  Properly align  the retaining
           rings with filter holder and secure by tighten-
           ing the three screw clamps.  Set the  zero
           level  of the manometer.  Attach the magnehelic
           gage to the sampler venturi quick  release
           connections.  Adjust the zero (if  needed)
           using the zero adjust  screw on  the face of
           the gage.
11.2.2.4   Turn the flow control  valve to  the fully open
           position and turn the  sampler on.   Adjust the
           flow control valve until  a magnehelic reading
           of approximately 70 in. is obtained.   Allow
           the magnehelic and manometer readings to
           stabilize and record these values.
11.2.2.5   Adjust the flow control valve and  repeat until
           six or seven uniformally spaced magnehelic
           readings are recorded  spanning  the range of
           approximately 40-70 in.  Record the readings
           on the Field Calibration Data Sheet (see
           Figure 9).  [Note: Use of some  filter/sorbent
           media combinations may restrict the airflow
           resulting in a maximum magnehelic  reading of
           60 in. or less.  In such cases, a  variable
           transformer should be  placed in-line  between
           the 110 volt power source and the  sampler so
           that the line voltage  can be increased suf-
           ficiently to obtain a maximum magnehelic
           reading approaching 70 in.].

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              T013-25

11.2.2.6  Adjust the orifice manometer reading  for  standard
          temperature and pressure using  the  following
          equation:
                  X =
-------
                      TO13-26
Mstd •
where:
V(M)(Pa)
Pstd
Tstd
Ta
                      Mstd = adjusted magnehelic reading to
                             standard temperature and pressure
                             (inches of water).
                      M    = observed magnehelic reading
                             (inches of water).
                      Pa   = ambient atmospheric pressure (mm Hg).
                      Pstd = standard pressure  (760 mm Hg).
                      Ta   = ambient temperature (K), (K = °C + 273),
                      Tstd = standard temperature (298 K).
        11.2.2.9   Plot each Mstd  value (y-axis)  versus its
                  associated Qstd  standard  (x-axis) on arithmetic
                  graph paper.  Draw a line of best fit between
                  the  individual  plotted points.  This is the
                  calibration curve for the venturi.  Retain with
                  sampler.
        11.2.2.10 Record the corresponding  Qstd  for each Mstd
                  under Qstd column on Field Calibration Data
                  Sheet, Figure 9.
11.2.3  Single-point Audit  of The High Volume Sampling System
        Utilizing Calibrated Flow Rate Transfer  Standard
        11.2.3.1   A single  point  flow audit check is  performed
                  before and after each sampling period utilizing
                  the  Calibration Flow Rate Transfer  Standard
                  (Section  11.2.1).
        11.2.3.2   Prior to  single point audit, a "dummy" adsorbent
                  cartridge and filter are  placed in  the sampling
                  head and  the  sampling motor  is activated.
                  The  flow  control valve  is fully opened and
                  the  voltage  variator  is  adjusted so that  a

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               T013-27

           sample  flow  rate  corresponding to 110% of the
           desired  flow rate (typically 0.20-0.28 m3/min)
           is  indicated on the  magnehelic gauge  (based on
           the previously obtained  multi-point calibration
           curve).   The motor is  allowed to warm up  for 5
           minutes  and  then  the flow control valve is
           adjusted to  achieve  the  desired flow  rate.
           Turn off the sampler.  The ambient temperature
           and barometric pressure  should be recorded on
           a Field Test Data Sheet  (Figure 10).
11.2.3.3   The flow rate transfer standard is placed on
           the sampli ng head.
11.2.3.4   Properly align the retaining  rings with filter
           holder and  secure by tightening the three screw
           clamps.
11.2.3.5   Using tubing, attach one manometer connector to
           the pressure tap  of  the  transfer  standard.   Leave
           the other connector  open to the atmosphere.
11.2.3.6   Adjust the manometer midpoint by  sliding  the
           movable scale until  the  zero  point corresponds
           with the water meniscus.  Gently  shake  or tap
           to remove any air bubbles and/or  liquid  remain-
           ing on tubing connectors.  (If  additional  liquid
           is required, remove  tubing connector  and  add
           clean water.)
11.2.3.7   Turn on high volume  motor and  let run for five
           minutes.
11.2.3.8   Record the pressure  differential  indicated, AH,
           in inches of water.   Be  sure  stable AH  has  been
           established.
11.2.3.9   Record the observed  magnehelic  gauge  reading,
           in inches of water.   Be  sure stable  M has been
           establi shed.

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                             T013-28

              11.2.3.10  Using previously established  Flow Rate  Transfer
                         Standard curve,  calculate Qg^d  (see  steps
                         11.2.2.6 - 11.2.2.7).
              11.2.3.11  Using previously established  venturi  calibration
                         curve, calculate the  indicated  QS^J  (Section
                         11.2.2.9).
              11.2.3.12  A multi-point  calibration of  the  Flow Rate
                         Transfer Standard against a primary  standard,
                         must be obtained annually, as outlined  in
                         Section 11.2.1.
              11.2.3.13  Remove Flow Rate Transfer Standard and  dummy
                         adsorbent cartridge and  filter  assembly.
11.3  Sample Collection
      11.3.1  After the sampling system has been  assembled and flow check-
              ed as described in Sections 11.1  and 11.2, it can  be used to
              collect  air samples, as described in Section 11.3.2.
      11.3.2  The samples should be located in  an unobstructed area, at
              least two meters from any obstacle  to air  flow.  The exhaust
              hose should be  stretched  out in  the downwind direction to
              prevent  recycling of air  into the sample head.
      11.3.3  With the empty  sample module removed from  the sampler,
              rinse all sample contact  areas using reagent grade hexane
              in a Teflon® squeeze bottle. Allow the  hexane  to  evaporate
              from the module before loading the  samples.
      11.3.4  Detach the lower chamber  of the  rinsed sampling  module.
              While wearing disposable  clean lint-free nylon  or  powder-
              free surgical gloves, remove a clean glass cartridge/sorbent
              from its container (wide  mouthed  glass jar with  a  Teflon®-
              lined lid) and  unwrap its aluminum  foil  covering.  The foil
              should be replaced back in  the sample container  to be re-
              used after the  sample has been collected.
      11.3.5  Insert the cartridge into the lower chamber  and  tightly
              reattach it to  the module.
      11.3.6  Using clean Teflon® tipped  forceps, carefully place a clean
              fiber filter atop the filter holder and  secure  in  place
              by clamping the filter holder ring  over  the  filter using
              the three screw clamps.  Insure  that all module  connec-
              tions are tightly assembled. [Note:  Failure to  do so

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                        T013-29
          could  result  in  air  flow  leaks  at poorly sealed locations
          which  could  affect sample representativeness].  Ideally,
          sample module  loading and unloading should be conducted
          in  a controlled  environment or  at least a centralized
          sample processing area  so that  the sample handling vari-
          ables  can  be minimized.
 11.3.7    With the module  removed from the sampler and the flow
          control valve  fully  open, turn  the pump on and allow it
          to  warm-up for approximately 5  minutes.
 11.3.8    Attach a "dummy" sampling module loaded with the exact
          same type  of filter  and sorbent media as that which
          will be used for sample collection.
 11.3.9    With the sampler off, attach the Magnahelic gage to the
          sampler.   Turn the sampler on and adjust the flow control
          valve  to the desired flow (normally as indicated by the
          cfm) magnahelic gauge reading and reference by the
          calibration chart.   [Note:  Breakthrough has not been a
          problem for all PAHs outlined in Section 1.5 using
          this sampling method except anthracene and penanthrene].
          Once the flow is properly adjusted, extreme care should
          be  taken not to inadvertantly alter its setting.
 11.3.10   Turn the smpler off and remove both the "dummy"  module
          and the Magnahelic gauge.  The sampler is now ready for
          field  use.
 11.3.11   The zero reading of the sampler Magnehelic is checked.
          Ambient temperature,  barometric pressure, elapsed time
          meter  setting, sampler serial  number,  filter number,
          and adsorbent sample  number are recorded on the  Field
         Test Data Sheet (see  Figure 10).  Attach the  loaded
          sampler module to the sampler.
 11.3.12  The voltage variator  and flow control  valve are  placed
         at the  settings used  in  Section 11.2.2,  and the  power
         switch  is turned  on.   The elapsed time meter  is  acti-
         vated and the start time is recorded.  The  flow  (Magne-
         helic setting)  is adjusted, if  necessary,  using  the
         flow control  valve.
11.3.13  The Magnehelic  reading  is recorded  every six  hours
         during  the  sampling period.  The calibration  curve

-------
                       T013-30

         (Section 11.2.4) is used to calculate the flow rate.
         Ambient temperature, barometric pressure, and  Magnehe-
         lic reading are recorded at the beginning and  end  of
         the sampling period.
11.3.14  At the end of the desired sampling  period, the power  is
         turned off.  Carefully remove the sampling head contain-
         ing the filter and adsorbent cartridge  to a .clean  area.
11.3.15  While wearing disposable lint free  nylon  or surgical
         gloves, remove the sorbent cartridge  from the  lower
         module chamber and lay it on the retained aluminum foil
         in which the sample was originally  wrapped.
11.3.16  Carefully remove the glass fiber filter from the upper
         chamber using clean Teflon® tiped forceps.
11.3.17  Fold the filter in half twice (sample side inward) and
         place it in the glass cartridge atop  the  sorbent.
11.3.18  Wrap the combined samples in aluminum foil and place  them
         in their original  glass sample container.  A sample label
         should be completed and affixed to  the  sample  container.
         Chain-of-custody should be maintained for all  samples.
11.3.19  The glass containers should be stored in  ice and pro-
         tected from light to prevent possible photo-decomposi-
         tion of collected analytes.  If the time  span  between
         sample collection and laboratory analysis is to exceed
         24 hours, sample must be kept refrigerated. [Note:  Recent
         studies (13,16) have indicated that PDF does not retain,
         during storage, B[a]P as effectively  as XAD-2.  Therefore,
         sample holding time should not exceed 20  days.]
11.3.20  A final calculated sample flow check  is performed  using
         the calibration orifice, as described in  Section 11.2.2.
         If calibration deviates by more than  10%  from  the  initial
         reading, the flow data for that sample  must be marked
         as suspect and the sampler should be  inspected and/or
         removed from service.
11.3.21  At least one field filter/adsorbent blank will be  re-
         turned to the laboratory with each  group  of samples.  A
         field blank is treated exactly as a sample except  that
         no air is drawn through the filter/adsorbent cartridge
         assembly.

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                                  T013-31
           11.3.22  Samples  are  stored  at 0°C  in  an  ice chest until receipt
                    at  the analytical  laboratory,  after which they are
                    refrigerated  at  4°C.
12.  Sample Clean-up and  Concentration
     [Note:  The following sample extraction,  concentration, solvent exchange
     and analysis procedures are  outlined for  user convenience in Figure 11.]
     12.1  Sample Identification
           12.1.1  The  samples  are returned  in the ice chest to the laboratory
                   in the glass  sample  container  containing the filter and
                   adsorbent.
           12.1.2  The  samples  are logged in the  laboratory logbook according
                   to sample location,  filter  and  adsorbent cartridge number
                   identification and total  air volume sampled (unconnected).
           12.1.3  If the time  span  between  sample registration and analysis
                   is greater than 24-hrs.,  then  the samples must be kept
                   refrigerated.   Minimize exposure  of samples to fluores-
                   cence  light.   All samples should  be extracted within one
                   week after sampling.
     12.2  Soxhlet Extraction and Concentration
           12.2*1  Assemble  the  Soxhlet apparatus  [see Figure 3(a)].  Immedi-
                   ately  before  use, charge  the Soxhlet apparatus with 200 to
                   250  ml of methylene  chloride and  reflux for 2 hours.  Let
                   the  apparatus  cool,  disassemble it, transfer the methylene
                   chloride  to  a  clean  glass container, and retain it as a
                   blank  for later analysis, if required.  Place the adsorbent
                   and  filter together  in the  Soxhlet apparatus (the use of an
                   extraction thimble  is optional) if using XAD-2 adsorbent in
                   the  sampling  module. [Note: The  filter and adsorbent are
                   analyzed  together in order  to  reach detection limits, avoid
                   questionable  interpretation of  the data, and minimize cost.]
                   Since  methylene chloride  is not a suitable solvent for PDF,
                   10%  ether in  hexane  is employed to extract the PAHs from
                   the  PUT resin  bed separate  from the methylene chloride
                   extraction of  the accompanying  filter  rather than methylene
                   chloride  for the  extraction of  the XAD-2 cartridge.
                   12.2.1.1   Prior to  extraction,  add a surrogate standard to
                             the  Soxhlet solvent.  A surrogate standard (i.e.,
                             a  chemically inert compound  not expected to

-------
                        T013-32
                   occur in  an environmental sample) should be
                   added to  each sample, blank, and matrix spike
                   sample just prior to extraction or processing.
                   The recovery of the surrogate standard is used
                   to monitor for unusual matrix effects, gross
                   sample processing errors, etc.  Surrogate recov-
                   ery is evaluated for acceptance by determining
                   whether the measured concentration falls within
                   the acceptance limits.  The following surrogate
                   standards have been successfully utilized in
                   determining matrix effects, sample process errors,
                   etc. utilizing GC/FID, GC/MS or HPLC analysis.
                   Surrogate                           Analytical
                   Standard          Concentration     Technique
                   Dibromobiphenyl       50 ng/uL         GC/FID
                   Dibromobiphenyl       50 ng/uL         GC/MS
                   Deuterated Standards 50 ng/uL         GC/MS
                   Decafluorobiphenyl   50 ng/uL         HPLC
                   [Note:  The deuterated standards will be added
                   in Section 14.3.2.  Deuterated analogs of selec-
                  tive PAHs cannot be used as surrogates for HPLC
                  analysis due to  coelution problems.] Add the
                   surrogate standard to the Soxhlet solvent.
        12.2.1.2  For the XAD-2  and filter extracted together,
                  add 300 mL of  methylene chlorine to  the apparatus
                  and reflux for 18 hours at a rate of at least
                  3 cycles per hour.
        12.2.1.3  For the PUF extraction separate from the filter,
                  add 300 mL of  10 percent ether in hexane to the
                  apparatus and  reflux for 18 hours at a rate of
                  at least 3 cycles  per hour.
        12.2.1.4  For the filter extraction, add 300 mL of methylene
                  chloride to the  apparatus and reflux for 18 hours
                  at a rate of  at  least 3 cycles per hour.
12.2.2  Dry the extract  from the Soxhlet  extraction by passing it
        through a drying column  containing about 10 grams of anhy-
        drous sodium sulfate.  Collect  the dried extract in  a
        Kuderna-Danish (K-D) concentrator assembly.  Wash the

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                             T013-33
              extractor flask and sodium sulfate column with 100 - 125 ml
              of methylene chloride to complete the quantitative transfer.
       12.2.3  Assemble a Kuderna-Danish concentrator [see Figure 3(b)]
              by attaching a 10 ml concentrator tube to a 500 ml evapora-
              tive flask.  [Note:  Other concentration devices (vortex
              evaporator) or techniques may be used in place of the K-D
              as long as qualitative and quantitative recovery can be
              demonstrated.]
       12.2.4  Add two boiling chips, attach a three-ball macro-Snyder
              column to the K-D flask, and concentrate the extract using
              a water bath at 60 to 65°C.  Place the K-D apparatus in  ,
              the water bath so that the concentrator tube is about half
              immersed in the water and the entire rounded surface of
              the flask is bathed with water vapor.  Adjust the vertical
              position of the apparatus and the water temperature as
              required to complete the concentration in  one hour.  At
              the proper rate of distillation, the balls of the column
              actively chatter but the chambers do not  flood.  When the
              liquid  has  reached an approximate volume  of 5 ml_, remove the
              K-D apparatus  from the water bath and allow the solvent
              to drain for at least 5  minutes  while cooling.
      12.2.5  Remove  the  Snyder  column and rinse the flask and its lower
              joint  into  the  concentrator tube with 5 ml of cyclohexane.
12.3  Solvent Exchange
      12.3.1  Replace the  K-D apparatus equipped with a  Snyder column
              back on the  water  bath.
      12.3.2  Increase the temperature of  the  hot water  bath  to 95-100°C.
              Momentarily, remove  the  Snyder column, add a  new boiling
              chip, and attach a two-ball  micro-Snyder column.  Prewet
              the Snyder column, using  1 ml of cyclohexane.   Place  the
              K-D apparatus on the water  bath  so that the  concentrator
              tube is  partially  immersed in the  hot water.  Adjust  the
              vertical position  of  the  apparatus and the water  tempera-
              ture, as required, to complete concentration  in  15-20
              minutes.  At the proper  rate of  distillation, the balls
              of the  column will actively  chatter, but the  chambers

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                             T013-34
              will  not  flood.   When the  apparent volume of liquid
              reaches 0.5  ml,  remove  the K-D  apparatus and allow it to
              drain and cool  for at least 10  minutes.
      12.3.3  When  the  apparatus is cool, remove the micro-Snyder
              column and  rinse its lower joint  into the concentrator
              tube  with about  0.2 ml  of  cyclohexane.  [Note:  A 5 ml
              syringe is  recommended  for this operation].  Adjust the
              extract volume  to exactly  1.0 mL  with cyclohexane.  Stopper
              the concentrator tube and  store refrigerated at 4°C, if
              further processing will  not be  performed immediately.  If
              the extract  will be stored longer than 24 hours, it should
              be transferred  to a Teflon®-sealed screw-cap vial.
12.4  Sample Cleanup By Solid Phase Exchange
      Cleanup procedures  may  not be needed for  relatively clean matrix
      samples.  If  the  extract in Section 12.3.3 is clear, cleanup may
      not be necessary.  If cleanup is not necessary, the cyclohexane
      extract ( 1 ml) can be  analyzed directly  by  GC/FI detection, except
      the initial oven  temperature begins at  30°C  rather than 80°C for
      cleanup samples (see Section 13.3), or  solvent exchange to aceton-
      itrile for HPLC analysis.  If cleanup is  required, the procedures
      are presented using either handpack silica gel column as prescribed
      in Method 610 (see Section 18.0, citation No.  18 and 22) or the
      use of a Lobar prepacked silica gel column for PAH concentration
      and separation.  Either approach can be employed by the user.
      12.4.1  Method 610 Cleanup Procedure [see Figure 3(c)]
              12.4.1.1   Pack  a 6-inch disposable Pasture pipette
                        (10 mm I.D.-x 7 cm length) with a piece of
                        glass wool.   Push the wool to the neck of the
                        disposable  pipette.   Add 10 grams of activated
                        silica gel  in methylene chloride slurry to the
                        disposable  pipette.   Gently tap the column to
                        settle the  silica gel and  elute the methylene
                        chloride.  Add 1 gram of anhydrous  sodium  sul-
                        fate  to the  top of the  silica gel  column.
              12.4.1.2  Prior to initial use, rinse the column  with
                        methylene chloride at 1 mL/min  for  1  hr  to

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                        T013-35
                   remove  any  trace  of contaminants.  Preelute the
                   column  with 40  ml of  pentane.  Discard the eluate
                   and  just  prior  to exposure  of the sodium sulfate
                   layer to  the  air, transfer  the 1 ml of the cyclo-
                   hexane  sample extract onto  the column, using an
                   additional  2  ml of cyclohexane to complete the
                   transfer.   Allow  to elute through the column.
         12.4.1.3   Just  prior  to exposure of the sodium sulfate
                   layer to  the  air, add 25 ml of pentane and con-
                   tinue elution of  the column.  Discard the pen-
                   tane  eluate.  [Note:  The pentane fraction
                   contains  the  aliphatic hydrocarbons collected
                   on the  filter/  adsorbent combination.  If inter-
                   ested,  this fraction may be analyzed for specific
                   aliphatic organics.]  Elute the column with 25 ml
                   of methylene  chloride/pentane (4 +6) (V/V) and
                   collect the eluate in a 500 ml K-D flask equipped
                   with  a  10 ml  concentrator tube.  [Note:   This
                   fraction contains the B[a]P and other moderately
                   polar PAHs].  Elution of the column should be
                   at a  rate of  about 2 mL/min.  Concentrate the
                   collected fraction to less than 10 ml by the
                   K-D technique, as illustrated in Section 12.3
                   using pentane to  rinse the walls of the  glass-
                  ware.  The extract is now ready for HPLC or GC
                  analysis.   [Note:   An additional  elution through
                  the column with 25 mL of methanol  will  collect
                  highly polar oxygenated PAHs with more than one
                  functional group.   This fraction may  be  analyzed
                  for specific polar PAHs.   However, additional
                  cleanup  by solid phase extraction may be required
                  to obtain  both qualitative and quantitative data
                  due to complexity  of  the  eluant.]
12.4.2  Lobar Prepacked Column Procedure
        12.4.2.1  The setup  using  the Lobar prepacked column  con-
                  sists of an  injection  port,  septum, pump,  pre-
                  column containing  sodium  sulfate,  Lobar  prepacked
                  column and solvent reservoir.

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                                 T013-36

                   12.4.2.2  The  column  is cleaned and activated according
                            to the  following  cleanup sequence:
                    Fraction         Solvent Composition           Volume (ml)
                       1       100%  Hexane                              20
                       2        80%  Hexane/20% Methylene Chloride       10
                       3        50%  Hexane/50% Methylene Chloride       10
                       4       100%  Methylene  Chloride                  10
                       5        95%  Methylene  Chloride/5% Methanol      10
                       6        80%  Methylene  Chloride/20% Methanol     10
                   12.4.2.3    Reverse  the sequence at the end of the run and
                              run to the 100%  hexane fraction in order to
                              activate the column.  Discard all fractions.
                   12.4.2.4    Pre-elute  the column with 40 ml of hexane,
                              which  is also discharged.
                   12.4.2.5    Inject 1 ml of the  cyclohexane sample extract,
                              followed by 1 ml injection of blank cyclohexane.
                   12.4.2.6    Continue elution of the column with 20 ml of
                              hexane,  which is also discharged.
                   12.4.2.7    Now elute  the column with 180 mL of a 40/60
                              mixture  of methylene chloride/hexane respectively.
                   12.4.2.8    Collect  approximately 180 ml of the 40/60 methy-
                              lene  chloride/hexane mixture in a K-D concentrator
                              assembly.
                   12.4.2.9    Concentrate to less than 10 ml with the K-D
                              assembly as discussed in Section 12.2.
                   12.4.2.10   The extract is now  ready for either HPLC or
                              GC  analysis.
13.  Gas Chromatography Analysis  with  Flame  lonization Detection
     13.1  Gas Chromatography  (GC)  is  a  quantitative  analytical technique
           useful for PAH identification.  This method provides the user the
           flexibility of column  selection  (packed or capillary)  and detector
           [flame ionization  (FI) or mass spectrometer  (MS)] selection.  The
           mass spectrometer provides  for specific identification  of B(a)P;
           however, with system  optimization,  other PAHs may be qualitatively
           and quantitatively  detected using MS  (see  Section 14.0).  This
           procedure provides  for common GC  separation  of the  PAHs with

-------
                             T013-37
      subsequent detection by either  FI  or MS  (see Figure  12.0).   The
      following PAHs have been quantified by GC separation with either
      FI or MS detection:
      Acenaphthene                     Chrysene
      Acenaphthylene                   Dibenzo(a,h)anthracene
      Anthracene                       Fluoranthene
      Benzo(a)anthracene               Fluorene
      Benzo(a)pyrene                   Indeno(l,2,3-cd)pyrene
      Benzo(b)f1uoranthene             Naphthalene
      Benzo(e)pyrene                   Phenanthrene
      Benzo(g,h,i)perylene             Pyrene
      Benzo(k)fluoranthene
      The packed column gas chromatographic method described here  can not
      adequately resolve the following four pairs  of compounds:  anthra'cene
      and phenanthrene; chrysene and  benzo(a)anthracene; benzo(b)fluoran-
      thene and benzo(k)fluoranthene;  and dibenzo(a,h)  anthracene  and
      indeno(l,2,3-cd)pyrene.  The use of a capillary column instead of
      the packed column, also described in this method, should adequately
      resolve these PAHs.  However, unless the purpose  of  the analysis can
      be served by reporting a quantitative sum for  an  unresolved  PAH pair,
      either capillary gas chromatography/mass spectroscopy (Section 14.0)
      or high performance liquid chromatography (Section 15.0) should be
      used for these compounds.  This  section  will  address the use of
      GC/FI detection using packed or  capillary columns.
13.2  To achieve maximum sensitivity with the  GC/FI  method, the extract
      must be concentrated to 1.0 ml,  if not already concentrated  to 1 ml.
      If not already concentrated to 1 ml, add a clean  boiling chip to the
      methylene chloride extract in the  concentrator tube.  Attach a two-
      ball micro-Snyder column.  Prewet  the micro-Snyder column by adding
      about 2.0 mL of methylene chloride to the top. Place the micro K-D
      apparatus on a hot water bath (60  to 65°C) so  that the concentrator
      tube is partially immersed in the  hot water.   Adjust the vertical
      position of the apparatus and the  water  temperature  as required to
      complete the concentration in 5  to 10 minutes. At the proper rate
      of distillation the balls will actively  chatter but  the chambers
      will  not flood.  When the apparent volume of liquid  reaches  0.5 ml,
      remove the K-D apparatus.  Drain and cool  for  at  least 10 minutes.
      Remove the micro-Snyder column and rinse its lower joint into the
      concentrator tube with a small volume of methylene chloride. Adjust
      the final  volume to 1.0 ml and stopper the concentrator tube.

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                                  TO13-38
     13.3  Assemble and  establish the  following  operating parameters for
           the GC equipped  with an FI  detector:
                              Capil lary
                        (A)                (B)
Identification
SPB-5 fused silica
capillary, 0.25 urn
5% phenyl, methyl
siloxane bonded
SPB-5 fused silica
capillary, 0.25 urn
5% phenyl, methyl
siloxane bonded
                                              Packed
Chromosorb W-AW-DMCS
(100/120 mesh) coated
with 3% OV-17
Dimensions

Carrier Gas

Carrier Gas
Flow Rate

Column
Program
Detector
30-m x 0.25-mm ID    30-m x 0.25-mm ID   1.8-m x 2-mm ID
Helium

28-30 cm/sec
( 1 cm/minute)
35°C for 2 min;
program at 8°C/min
to 280°C and hold
for 12 minutes
Heli urn

28-30 cm/sec
( 1 cm/minute)
80°C for 2 min;
program at 8°C/min
to 280°C and hold
for 12 minutes
Nitrogen

30-40 cm/minute
Hold at 100°C for
4 minutes; program at
8°C/min to 280°C and
hold for 15 minutes
Flame lonization     Flame lonization    Flame lonization
(A) Without column cleanup (see Section 12.4)   ~~~~
(B) With column cleanup (see Section 12.4.1)

     13.4  Prepare and calibrate the chromatographic system using either
           the external standard technique (Section 13.4.1) or the internal
           standard technique (Section 13.4.2).  Figure 13.0 outlines the
           following sequence involving GC calibration and retention time
           window determination.
           13.4.1  External Standard Calibration Procedure - For each analyte
                   of interest, including surrogate compounds for spiking, if
                   used, prepare calibration standards at a minimum of five
                   concentration levels by adding volumes of one or more stock
                   standards to a volumetric flask and diluting to volume with
                   methylene chloride.  [Note:  All calibration standards of
                   interest involving selected PAHs, of the same concentration,

                   can be  prepared in the same flask.]
                   13.4.1.1  Prepare stock standard solutions at a concentration
                             of 100 ug/uL by dissolving 0.100 gram of assayed PAH
                             material in methylene chloride and diluting to vol-
                             in a 10 ml volumetric flask.  [Note: Larger volumes

                             can be used at the convenience of the analyst.]

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               T013-39
 13.4.1.2  When compound purity is assayed to be 98% or
          greater, the weight can be used without correc-
          tion to calculate the concentration of the stock
          standard. [Note:  Commercially prepared stock
          standards can be used at any concentration if
          they are certified by the manufacturer or by an
          independent source.]  Transfer the stock standard
          solutions into Teflon®-sealed screw-cap bottles.
 13.4.1.3  Store at 4°C and protect from light.  Stock
          standards should be checked frequently for signs
          of degradation or evaporation, especially just
          prior to preparing calibration standards from
          them.  Stock standard solutions must be replaced
          after one year, or sooner, if comparison with
          check standards indicates a problem.
 13.4.1.4  Calibration standards at a minimum of five
          concentration levels should be prepared through
          dilution of the stock standards with methylene
          chloride.   One of the concentration levels should
          be at a concentration near, but above, the method
          detection  limit.  The remaining concentration
          levels  should correspond to the expected range
          of concentrations found  in real  samples or
          should  define the working range of the GC.
          [Note:  Calibration solutions  must be replaced
          after six  months, or sooner,  if comparison
          with a  check standard  indicates a problem.]
13.4.1.5  Inject  each  calibration  standard using the
          technique  that will  be used to introduce the
          actual  samples  into  the  gas chromatograph
          (e.g.,  1-  to 3-uL injections).  [Note:   The
          same amount  must be  injected  each  time.]
13.4.1.6  Tabulate peak  height  or  area  responses against
          the mass injected.   The  results can  be used to
          prepare  a  calibration curve for each  analyte.
          [Note:   Alternatively, for  samples that  are
          introduced into  the  gas  chromatograph  using a
          syringe, the ratio of the  response to  the  amount

-------
                       T013-40

                  injected,  defined  as  the  calibration  factor  (CF),
                  can  be  calculated  for each analyte at each stand-
                  ard  concentration  by  the  following equation:
           Calibration factor  (CF) = 	Total Area of  Peak
                                    Mass injected  (in  nanograms)
                  If the  percent  relative standard  deviation
                  (%RSD)  of  the calibration factor  is less than
                  20%  over the working  range,  linearity through
                  the  origin can  be  assumed, and the average
                  calibration factor can be used in place of a
                  calibration curve.]
        13.4.1.7   The  working calibration curve or  calibration
                  factor  must be  verified on each working day  by
                  the  injection of one  or more calibration
                  standards.  If  the response  for any analyte
                  varies  from the predicted response by more
                  than +20%, a new calibration curve must be
                  prepared for that  analyte.   Calculate the
                  percent variance by the following equation:
                    Percent  variance =  R? - RI x 100
                                         Rl
                  where
                    Rg =  Calibration factor from succeeding analysis.
                    R! =  Calibration factor from first  analysis.
13.4.2  Internal  Standard Calibration  Procedure -  To use this
        approach, the  analyst must select one  or more internal
        standards that are similar in analytical behavior to the
        compounds of interest.  The  analyst must further  demon-
        strate that the measurement  of  the  internal standard is
        not affected by method or matrix interferences.  Due to
        these limitations, no  internal  standard applicable to
        all samples can be suggested.   [Note:   It  is recommended
        that the  internal standard approach be used only  when  the
        GC/MS procedure is employed  due to  coeluting species.]

-------
               T013-41

13.4.2.1  Prepare calibration standards  at a minimum of
          five concentration levels  for  each analyte of
          interest by adding volumes of  one or more stock
          standards to a volumetric  flask.
13.4.2.2  To each calibration standard,  add a  known con-
          stant amount of one or more internal standard
          and dilute to volume with  methylene  chloride.
          [Note:  One of the standards should  be at a
          concentration near, but above, the method
          detection limit.  The other concentrations
          should correspond to the expected range of
          concentrations found in real samples or should
          define the working range of the detector.]
13.4.2.3  Inject each calibration standard using the same
          introduction technique that will be  applied to
          the actual samples (e.g.,  1- to 3-uL injection).
13.4.2.4  Tabulate the peak height or area responses against
          the concentration of each  compound and internal
          standard.
13.4.2.5  Calculate response factors (RF) for each compound
          as follows:
            Response Factor (RF) = (AsCis)/(A-jsCs)
          where:
            As  = Response for the analyte to  be measured
                  (area units or peak height).
            ATS = Response for the internal standard.
                  (area units or peak height).
            C-jS = Concentration of the internal standard,
                  (ug/L).
            Cs =  Concentration of the analyte to be
                  measured, (ug/L).
13.4.2.6  If the RF value over the working range is con-
          stant (<20% RSD), the RF can be assumed to be
          invariant, and the average RF  can be used for
          calculations.  [Note:  Alternatively, the results
          can be used to plot a calibration curve of
          response ratios, As/AiS versus RF.]

-------
                             T013-42

              13.4.2.7  The working calibration curve or RF must  be  veri-
                        fied on each working day by the measurement  of
                        one or more calibration standards.
              13.4.2.8  If the response for any analyte varies  from  the
                        predicted response by more than +20%, a new  cali-
                        bration curve must be prepared  for  that compound.
13.5  Retention Time Windows Determination
      13.5.1  Before analysis can be performed, the retention time windows
              must be established for each analyte.
      13.5.2  Make sure the GC system is within optimum operating condi-
              tions.
      13.5.3  Make three injections of the standard containing  all
              compounds for retention time window determination.  [Note:
              The retention time window must be established for each
              analyte throughout the course of a 72-hr  period.]
      13.5.4  The retention window is defined as plus or minus  three
              times the standard deviation of the absolute  retention
              times for each standard.
      13.5.5  Calculate the standard deviation of the three absolute
              retention times for each single component standard. In
              those cases where the standard deviation  for  a particular
              standard is zero, the laboratory must substitute  the
              standard deviation of a close eluting, similar compound
              to develop a valid retention time window.
      13.5.6  The laboratory must calculate retention time  windows for each
              standard on each GC column and whenever a new GC  column
              is installed.  The data must be noted and retained  in  a
              notebook by the laboratory as part of the user SOP  and
              as a quality assurance check of the analytical system.
13.6  Sample Analysis
      13.6.1  Inject 1- to 3-uL of the methylene chloride extract from
              Section 13.2 (however, the same amount each time) using
              the splitless injection technique when using  capillary
              column.  [Note: Smaller (1.0 uL) volumes  can  be injected
              if automatic devices are employed.]

-------
                       T013-43

13.6.2  Record the volume injected  and  the  resulting peak  size
        in area units or peak  height.
13.6.3  Using either the internal  or external  calibration  pro-
        cedure, determine the  identity  and  quantity of  each com-
        ponent peak in the sample  chromatogram through  retention
        time window and established calibration  curve.   Table 2
        outlines typical  retention  times  for selected PAHs, using
        both the packed and capillary column technique  coupled
        with FI detection, while Figure 14.0 illustrates typical
        chromatogram for a packed  column  analysis.
        13.6.3.1  If the responses  exceed the linear  range of
                  the system,  dilute the  extract and  reanalyze.
                  It is recommended that  extracts be diluted so
                  that all peaks are on scale.  Overlapping
                  peaks are not  always  evident when peaks  are off
                  scale.  Computer  reproduction  of chromatograms,
                  manipulated  to ensure all peaks are on scale
                  over a 100-fold  range,  are acceptable if linearity
                  is demonstrated.   Peak  height  measurements are
                  recommended  over  peak area integration when over-
                  lapping peaks  cause errors in  area  integration.
        13.6.3.2  Establish daily retention time windows for each
                  analyte.  Use  the absolute retention  time for
                  each analyte from Section 13.5.4 as the  midpoint
                  of the window  for that  day. The daily retention
                  time window  equals the  midpoint j^ three  times the
                  standard deviation determined  in Section 13.5.4.
        13.6.3.3  Tentative identification  of an analyte occurs
                  when a peak  from  a sample extract falls  within
                  the daily retention time  window.  [Note: Con-
                  firmation may  be  required on a second GC column,
                  or by GC/MS  (if concentration  permits) or by
                  other recognized  confirmation  techniques if
                  overlap of peaks  occur.]
        13.6.3.4  Validation of  GC  system qualitative  performance
                  is performed through  the  use of the midlevel
                  standards.  If the mid-level standard falls out-
                  side its daily retention  time  window, the system

-------
                                  T013-44
                             is out  of control.   Determine  the  cause  of the
                             problem and perform a  new calibration sequence
                             (see Section 13.4).
                   13.6.3.5  Additional  validation  of  the GC  system perform-
                             ance is determined  by  the surrogate  standard
                             recovery.  If the recovery of  the  surrogate
                             standard deviates from 100% by not more  than
                             20%, then the sample extraction, concentration,
                             clean-up and analysis  is  certified.  If  it
                             exceeds this value,  then  determine the cause
                             of the  problem and  correct.
           13.6.4  Determine  the concentration of each analyte  in the sample
                   according  to Sections  17.1 and 17.2.1.
14.  Gas Chromatography with  Mass Spectroscopy Detection
     14.1  The analysis of  the  extracted  sample  for benzo[a]pyrene and other
           PAHs is accomplished by an electron impact  gas chromatography/mass
           spectrometry (El GO/MS) in the selected  ion monitoring (SIM) mode
           with a total  cycle time (including voltage  reset time) of one
           second or less.  The GC is equipped with an ultra  No.  2 fused
           silica capillary column (50-m  x 0.25-mm  I.D.) with helium  carrier
           gas for analyte  separation. The GC column  is temperature  controlled
           and interfaced directly to the MS ion  source.
     14.2  The laboratory must  document that the  El  GC/MS system  is properly
           maintained  through periodic calibration  checks.  The GC/MS system
           should have the  following specifications:
             Mass range:  35-500 amu
             Scan time:   1 sec/scan
             GC Column:  50 m x 0.25 mm I.D. (0.25  urn  film thickness)
               Ultra No. 2  fused silica capillary column or equivalent
             Initial  column temperature and hold  time:  40°C  for  4 min
             Column temperature program:   40-270°C  at  10°C/min
             Final  column temperature hold:  270°C  (until benzo[g,h,i] perylene
               has eluted)
             Injector temperature:   250-300°C
             Transfer  line  temperature:   250-300°C
             Source temperature:   According to manufacturer's specifications
             Injector:   Grob-type, splitless
             El Condition:  70  eV
             Mass Scan:  Follow manufacturer instruction for  select ion
               monitoring (SIM) mode.                        ,
             Sample volume:   1-3  uL
             Carrier gas:   Helium at 30 cm/sec.

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                             T013-45

      The GC/MS is tuned  using  a  50 ng/uL  solution  of decafluorotriphenyl-
      phosphine (DFTPP).   The DFTPP permits the user to tune the mass spec-
      trometer on a daily basis.   If  properly tuned, the DFTPP  key ions
      and ion abundance criteria  should  be met as outlined in Table 3.
14.3  The GC/MS operating conditions  are outlined in Table 4.   The
      GC/MS system can be calibrated  using the external standard tech-
      nique (Section 14.3.1)  or the internal standard technique
      (Section 14.3.2).  Figure 15.0  outlines the following sequence
      involving the GC/MS calibration.
      14.3.1  External standard calibration procedure.
              14.3.1.1 Prepare calibration standard of B[a]P or other,
                       PAHs  at a minimum  of five concentration levels
                       by adding volumes  of one or more stock  standards
                       to a  volumetric  flask and diluting to volume
                       with  methylene chloride.  The stock standard
                       solution  of B[a]P  (1.0 ug/uL) must be prepared
                       from  pure standard materials or purchased as
                       certified solutions.
              14.3.1.2 Place 0.0100  grams of native B[a]P or other PAHs
                       on a  tared aluminum weighing disk and weigh on
                       a Mettler balance.
              14.3.1.3 Quantitatively,  transfer to a 10 ml volumetric
                       flask.  Rinse the  weighing  disk with several
                       small portions of  methylene chloride.   Ensure
                       all material  has been transferred.
              14.3.1.4 Dilute  to mark with methylene chloride.
              14.3.1.5 The concentration  of the stock standard solution
                       of B[a]P  or other  PAHs in the flask is  1.0 ug/uL
                       [Note:  Commerically prepared stock standards may
                       be used at any concentration if they are certified
                       by the  manufacturer or by an independent source.]
              14.3.1.6 Transfer  the  stock standard solutions into Teflon®-
                       sealed  screw-cap bottles.   Store at 4°C and pro-
                       tect  from light.   Stock standard solutions should
                       be checked frequently for signs of degradation or
                       evaporation, especially just prior to preparing
                       calibration standards from them.

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               T013-46
14.3.1.7  Stock standard solutions must be replaced  after
          1 yr or sooner if comparison with quality  control
          check samples indicates a problem.
14.3.1.8  Calibration standards at a minimum of five con-
          centration levels should be prepared.  [Note:
          One of the calibration standards should be at  a
          concentration near, but above the method detection
          limit; the others should correspond to the range
          of concenrations found in the sample but should not
          exceed the working range of the  GC/MS system.]
          Accurately pipette 1.0 ml  of the stock solution
          (1 ug/uL)  into another 10 ml volumetric flask,
          dilute to  mark with methylene chloride. This
          daughter solution contains 0.1 ug/uL of B[a]P
          or other PAHs.
14.3.1.9  Prepare a  set of standard solutions by appropri-
          ately diluting, with methylene chloride, accu-
          rately measured volumes of the daughter solution
          (0.1 ug/uL).
14.3.1.10 Accurately pipette 100 uL, 300 uL, 500 uL, 700 uL
          and 1000 uL of the daughter solution (0.1  ug/uL)
          into each  10 ml volumetric flask, respectively.
          To each of these flasks, add an  internal deuterated
          standard to give a final concentration of  40
          ng/uL of the internal deuterated standard  (Section
          14.3.2.1).  Dilute to mark with  methylene  chloride.
14.3.1.11 The concentration of B[a]P in each flask is 1  ng/uL,
          3 ng/uL, 5 ng/uL, 7 ng/uL, and 10 ug/uL respec-
          tively.  All standards should be stored at 4°C
          and protected from fluorescent light and should
          be freshly prepared once a week  or sooner  if check
          standards  indicates a problem.
14.3.1.12 Analyze a  constant volume (1-3 uL) of each cali-
          bration standard and tabulate the area responses
          of the primary characteristic ion of each  stand-
          ard against the mass injected.  The results may
          be used to prepare a calibration curve for each
          compound.   Alternatively, if the ratio of  response

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                        T013-47
                   to amount injected (calibration factor) is a
                   constant over the working range (<20% relative
                   standard deviation, RSD), linearity through the
                   origin may be assumed and the average ratio or
                   calibration factor may be used in place of a
                   calibration curve.
         14.3.1.13 The working calibration curve or calibration
                   factor must be verified on each working day
                   by the measurement of one or more calibration
                   standards.   If the response for any parameter
                   varies from the predicted response by more than
                   ± 20%, the  rest must  be repeated using a  fresh
                   calibration standard.  Alternatively,  a new
                   calibration  curve or  calibration factor must
                   be prepared  for that  compound.
14.3.2  Internal  standard  calibration procedure.
         14.3.2.1  To use  this  approach,  the analyst  must  select
                   one or  more  internal  standards  that  are similar
                   in analytical  behavior to the compounds of  inter-
                   est.  For analysis  of B[a]P, the analyst should
                   use perylene -di2.  The  analyst must further demon-
                   strate  that the measurement of  the  internal standard
                   is  not  affected by method  or matrix interferences.
                   The following  internal standards are suggested
                   at  a  concentration of  40  ng/uL  for specific PAHs:
                   Perylene -dip               Acenaphthene - dm
                   Benzo(a)pyrene               Acenaphthene
                   Benzo(k)fluoranthene         Acenaphthylene
                   Benzo(g,h,i)perylene         Fluorene
                   Dibenzo(a,h)anthracene
                   Indeno(l,2,3-cd)pyrene       Naphthalene - d«
                   Chrysene - di?               Naphthalene
                  Benzo(a)anthracene           Phenanthrene -dm
                  Chrysene
                  Pyrene                       Anthracene
                                               Fluoranthene
                                               Phenanthrene
        14.3.2.2   A mixture of the above deuterated compounds in
                  the appropriate concentration  range are cooer-
                  cially available (see  Section  9.3.1.5).

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                T013-48
14.3.2.3  Use the base peak  ion  as  the  primary  ion  for
          quantification  of  the  standards.   If  interferences
          are noted,  use  the next two most  intense  ions
          as  the secondary ions.  The internal  standard
          is  added to all  calibration standards and all
          sample extracts  analyzed  by GC/MS.  Retention
          time standards,  column  performance  standards,
          and a mass  spectrometer tuning  standard may be
          included in the  internal  standard solution used.
 14.3.2.4 Prepare calibration standards at  a  minimum of
          three concentration level  for each  parameter of
          interest by adding appropriate volumes of one
          or  more stock standards to a  volumetric flask.
          To  each calibration standard  or standard  mixture,
          add a known constant amount of one  or more of the
          internal  deuterated standards to  yield a  resulting
          concentration of 40 ng/uL of  internal  standard
          and dilute  to volume with methylene chloride.
          One of the  calibration  standards  should be at a
          concentration near, but above,  the  minimum detec-
          tion limit  (MDL) and the  other concentrations
          should correspond  to the  expected range of
          concentrations  found in real  samples  or should
          define the  working range  of the GC/MS system.
 14.3.2.5 Analyze constant amount (1-3  uL)  of each  calibra-
          tion standard and  tabulate the area of the
          primary characteristic  ion against  concentration
          for each compound  and  internal  standard,  and
          calculate the response  factor (RF)  for each analyte
          using the following equation:
             RF  = (AsCis)/(AisCs)
          Where:
              As = Area of the characteristic ion for the
                   analyte to be measured.
             A-js = Area of the characteristic ion for the
                   internal  standard.
             Cis = Concentration  of the internal standard,
                   (ng/uL).
              Cs = Concentration of the analyte to  be
                   measured, (ng/uL).

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                             T013-49

                       If the RF value over the working range is a con-
                       stant (<20% RSD), the RF can be assumed to be'
                       invariant and the average RF can be used for
                       calculations.  Alternatively, the results can
                       be used to plot a calibration curve of response
                       ratios, As/A-js, vs. RF.   Table 5.0 outlines key
                       ions for selected internal  deuterated  standards.
              14.3.2.6 The working calibration  curve or RF must be veri-
                       fied on each working day by the measurement of one
                       or more calibration standards.  If the response
                       for any parameter varies from the predicted response
                       by more than _+ 20%, the  test must be repeated  using
                       a fresh calibration standard.  Alternatively,  a
                       new calibration curve must  be prepared.
              14.3.2.7 The relative retention times for each  compound
                       in each calibration run  should agree within
                       0.06 relative retention  time units.
14.4  Sample Analysis
      14.4.1  It is highly recommended that the extract be screened on a
              GC/FID or GC/PID using the same type of capillary column
              as in the GC/MS procedure.  This  will minimize  contamina-
              tion of the GC/MS system from unexpectedly high concentra-
              tions of organic compounds.
      14.4.2  Analyze the 1 ml extract (see Section 13.2)  by  GC/MS.
              The recommended GC/MS operating conditions to be used
              are specified in Section 14.2.
      14.4.3  If the response for any quantisation ion exceeds the
              initial  calibration curve range of the GC/MS system,
              extract dilution must take place.  Additional  internal
              standard must be added to the diluted extract to maintain
              the required  40 ng/uL of each internal  standard in the
              extracted volume.  The diluted  extract must  be  reanalyzed.
      14.4.4  Perform all  qualitative and  quantitative measurements as
              described in  Section 14.3.   The typical  characteristic  ions
              for selective PAHs are outlined in Table 6.0.   Store the
              extracts at 4°C, protected from light in screw-cap vials
              equipped with unpierced Teflon®-li ned,  for future analysis.

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                             T013-50


      14.4.5 For sample analysis, the comparison between the sample  and

             references spectrum must illustrate:

             (1)  Relative intensities of major ions  in the reference
             spectrum (ions >10% of the most abundant ion)  should be
             present in the sample spectrum.

             (2)  The relative intensities of the  major ions should
             agree within +20%.  (Example:  For an ion with an  abundance
             of 50% in the standard spectrum, the  corresponding sample
             ion abundance must be between 30 and  70%).

             (3)  Molecular ions present in the reference spectrum
             should be present in the sample spectrum.

             (4)  Ions present in the sample spectrum but not  in the
             reference spectrum should be reviewed for possible back-
             ground contaminatiuon or presence of  coeluting compounds.

             (5)  Ions present in the reference spectrum but not in
             the sample spectrum should be reviewed for possible sub-
             traction from the sample spectrum because of background
             contamination or coeluting peaks.  Data  system library  re-
             duction programs can sometimes create these discrepancies.

      14.4.6 Determine the concentration of each analyte in the sample

             according to Sections 17.1 and 17.2.2.

14.5  GC/MS Performance Tests

      14.5.1 Daily DFTPP Tuning - At the beginning of each  day  that

             analyses are to be performed, the GC/MS  system must be

             checked to see that acceptable performance criteria are
             achieved when challenged with a 1 uL  injection volume

             containing 50 ng of decafluorotriphenylphosphine  (DFTPP).
             The DFTPP key ions and ion abundance  criteria  that must

             be met are illustrated in Table 3.0.   Analysis should not

             begin until all those criteria are met.   Background

             subtraction should be staightforward  and designed  only  to

             eliminate column bleed or instrument  background ions.

             The GC/MS tuning standard should also be used  to  assess
             GC column performance and injection port inertness.
             Obtain a background correction mass spectra of DFTPP and
             check that all key ions criteria are  met.  If  the  criteria

             are not achieved, the analyst must retune the  mass spectrometei

             and repeat the test until all criteria are achieved. The

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                        TO13-51

        performance  criteria must  be  achieved  before  any  samples,
        blanks on  standards are  analyzed.   If  any  key ion  abundance
        observed for the daily DFTPP  mass  tuning check differs by
        more than  10% absolute abundance  from  that observed during
        the previous daily tuning, the  instrument must be  retuned
        or the sample and/or calibration  solution  reanalyzed until
        the above  condition is met.
14.5.2  Daily 1-point Initial Calibration  Check -  At  the  beginning
        of each work day, a daily  1-point  calibration check is
        performed  by re-evaluating the  midscale calibration
        standard.  This  is the same  check  that is  applied  during
        the initial  calibration, but  one  instead of  five working
        standards  are evaluated.  Analyze  the  one  working  standards
        under the  same conditions  the initial  calibration  curve
        was evaluated.  Analyze  1  uL  of each of the mid-scale
        calibration  standard and tabulate  the  area response of
        the primary  characteristic ion  against mass  injected.
        Calculate  the percent difference  using the following
        equation:
         % Difference =  RFr - RFT  x  100
                          RFj
         Where: 	
                RFj  = average  response  factor  from initial cali-
                      bration using  mid-scale  standard.
               RFC  = response factor from current verification  check
                      using mid-scale standard.
        If the percent difference  for the  mid-scale  level  is
        greater than 10%, the  laboratory  should consider  this  a
        warning limit.  If the percent  difference  for the  mid-scale
        standard is  less than 20%, the  initial calibration is
        assumed to be valid.   If the  criterion is  not met  (<20%
        difference), then corrective  action MUST be  taken. [Note:
        Some possible problems are standard mixture  degradation,
        injection  port inlet contamination, contamination  at the
        front end  of the analytical  column, and active sites in  the
        column or  chromatographic  system.] This check must be met

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                                 T013-52
                  before  analysis begins.   If no source of the problem can be
                  determined  after corrective action has been taken, a new
                  five-point  calibration MUST be generated.  This criterion
                  MUST  be met before sample analysis begins.
          14.5.3   12-hour Calibration Verification - A calibration standard
                  at  mid-level concentration containing B[a]P or other PAHs
                  must  be performed every twelve continuous hours of analysis.
                  Compare the standard every 12-hours with the average response
                  factor  from the initial calibration.  If the % difference
                  for the response factor (see Section 14.5.2) is less than
                  20%,  then the GC/MS system is operative within initial cali-
                  bration values.  If the criteria is not met (>20% difference),
                  then  the source of the problem must be determined and a new
                  five-point  curve MUST be  generated.
          14.5.4   Surrogate Recovery - Additional validation of the GC system
                  performance is determined by the surrogate standard recovery.
                  If  the  recovery of the surrogate standard deviates from 100%
                  by  not  more than 20%, then the sample extraction, concentra-
                  tion, clean-up and analysis is certified.  If it exceeds this
                  value,  then determine the cause of the problem and correct.
15.   High Performance Liquid  Chromatography (HPLC) Detection
    15.1   Introduction
          15.1.1   Detection of B[a]P by HPLC has also been a viable tool in
                  recent  years.  The procedure outlined below has been writ-
                  ten specifically for analysis of B[a]P by HPLC.  However, by
                  optimizing  chromatographic conditions [(multiple detector
                  fluorescence - excitation at 240 nm, emission at 425  nm; ul-
                  traviolet at 254 nm)] and varying  the mobile phase composi-
                  tion  through a gradient  program, the following PAHs may
                  also  be quantitatified:
COMPOUND
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo( b ) f 1 uoranthene
Benzo[e]pyrene
Benzo(ghi jperylene
±UV= Ultraviolet
FL= Fluorescences
DETECTOR1
UV
UV
UV
FL
FL
FL
FL
FL

COMPOUND
Benzo(k) f 1 uoranthene
Dibenzo(a,h)anthracene
Fl uoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene

DETECTOR1
FL
FL
FL
UV
FL
UV
UV
FL


-------
                              T013-53

     15.1.2  This method provides quantitative identification of the se-
             lected PAH's compounds listed above by high performance liquid
             chromatography.  It is based on separating of compounds of
             a liquid mixture through a liquid chromatographic column and
             measuring the separated components with suitable detectors.
     15.1.3  The method involves solvent exchange, with subsequent HPLC
             detection involving ultraviolet (UV) and fluoresence (FL)
             detection.
15.2  Solvent Exchange To Acetonitrile
     15.2.1  To the extract in the concentrator tube, add 4 ml of ace-
             tonitrile and a new boiling chip;  attach a micro-snyder
             column to the apparatus.
     15.2.2  Increase temperature of the hot water bath to  95 to 100°C.
     15.2.3  Concentrate the solvent as in Section 12.3.
     15.2.4  After cooling, remove the micro-Snyder column  and rinse its
             lower sections into the concentration tube with approxi-
             mately 0.2 mL acetonitrile.
     15.2.5  Adjust its volume to 1.0  mL.
15.3 HPLC Assembly
     15.3.1  The  HPLC  system is  assembled,  as illustrated in Figure  10.
     15.3.2  The  HPLC  system is  operated according to the following  para-
             meters:
                              HPLC  Operating Parameters
               Guard Column:         VYDAC  201 GCCIOYT
               Analytical  Column:    VYDAC  201 TP5415  C-18 RP (0.46 x  25  cm)
               Column  Temperature:   27.0 >2°C
               Mobile  Phase:           Solvent Composition        Time  (Minutes)
                                    40%  Acetonitrile/60% water        0
                                  100%  Acetonitrile                  25
                                  100%  Acetonitrile                  35
                                    40%  Acetonitrile/60% water       45
                           Linear gradient elution at 1.0 mL/min
               Detector:   Variable wavelength ultraviolet  and  fluore-
                           scence.
               Flow Rate:  1.0 mL/minute

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                             T013-54

            [Note:  To prevent irreversible absorption due to "dirty"
            injections and premature loss of column efficiency, a
            guard column is installed between the injector and the
            analytical column.  The guard column is generally packed
            with  identical material as is found in the analytical
            column.  The guard column is generally replaced with a
            fresh guard column after several injections ( 50) or
            when  separation between compounds becomes difficult.
            The analytical column  specified in this procedure has
            been  laboratory evaluated.  Other analytical columns
            may be used as long as they meet procedure and separation
            requirements.  Table 7.0 outlines other columns uses to
            determine PAHs by HPLC.]
     15.3.3  The mobile phases are  placed in separate HPLC solvent
            reservoirs and the pumps are set to yield a total of
            1.0 mL/minute and allowed to pump for 20-30 minutes
            before the first analysis.  The detectors are switched on
            at least  30 minutes before the  first analysis.  UV Detec-
            tion  at 254 nm is generally preferred.  The fluorescence
            spectrometer  excitation wavelengths  range from 250 to 800
            nanometers.   The excitation and emission  slits are both
            set  at 10 nanometers nominal bandpass.
     15.3.4  Before each analysis,  the detector  baseline is checked
            to  ensure stable  operation.
15.4 HPLC Calibration
     15.4.1  Prepare  stock standard solutions  at PAH  concentrations  of
            1.00 ug/uL  by dissolving 0.0100 grams  of  assayed  material  in
             acetonitrile  and  diluting to  volume in  a  10 mL volumetric
             flask.   [Note: Larger  volumes  can be used at  the  convenience
     •  • -J    of  the  analyst.   When  compound purity is  assayed to  be  98%
             or greater, the weight can  be  used  without  correction to
             calculate the concentration  of the  stock  standard.]   Commer-
             cially prepared  stock  standards can be used at  any concen-
             tration  if  they  are certified  by the manufacturer or by an
             independent source.

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                          T013-55
 15.4.2   Transfer the  stock  standard solutions  into Teflon®-sealed
         screw-cap bottles.  Store at 4°C and protect from light.
         Stock  standards  should  be checked frequently for signs of
         degradation or evaporation, especially just prior to pre-
         paring  calibration  standards from them.
 15.4.3   Stock  standard solutions must be replaced after one year, or
         sooner,  if comparision with check standards indicates a problem.
 15.4.4   Prepare  calibration standards at a minimum of five concentra-
         tion levels ranging from 1 ng/uL to 10 ng/uL by first diluting
         the stock  standard  10:1 with acetonitrile, giving a daughter
         solution of 0.1  ug/uL.  Accurately pipette 100 uL, 300 uL,
         500 uL,  700 uL and  1000 uL of the daughter solution (0.1 ug/uL)
         into each  10 ml  volumetric flask, respectively.  Dilute to
         mark with  acetonitrile.  One of the concentration levels
         should be  at a concentration near, but above, the method
         detection  limit  (MDL).  The remaining concentration levels
         should correspond to the expected range of concentrations
         found in  real  samples  or should define the working range
         of the HPLC.  [Note:  Calibration standards must be replaced
         after six months, or sooner, if comparison with check standards
         indicates a problem.]
15.4.5  Analyze  each calibration standard (at lease five levels)
        three times.  Tabulate area  response vs.  mass  injected.
        All calibration runs are performed  as described for sample
        analysis in Section 15.5.1.   Typical  retetion times  for
        specific PAHs  are illustrated  in Table  8.0.   Linear response
        is indicated where a correlation coefficient  of at  least
        0.999 for a linear least-squares fit  of the  data (concen-
        tration versus area  response)  is obtained.   The retention
        times  for each analyte should  agree within +_ 2%.
15.4.6  Once  linear response has been  documented,  an  intermediate  con-
        centration standard  near the  anticipated  levels  for  each com-
        ponent,  but at least 10  times the detection  limit,  should  be
        chosen  for a daily calibration check.   The  response  for the
        various  components should be within 15% day to  day.   If greater
        variability is observed,  recalibration may be required or  a
        new calibration curve must be developed from fresh standards.

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                              T013-56

     15.4.7  The response  for  each  component  in the daily calibration
             standard is used  to  calculate a  response factor according to
             the following  equation:
                                   RFC  = Cr  x VT
                                           RC
             Where
                 RFC =  response  factor  (usually area counts) for the
                        component of interest in nanograms injected/
                        response  unit.
                 Cc   =  concentration  (mg/L)  of analyte in the daily
                        calibration standard.
                 Vj   =  volume (uL) of calibration standard injected.
                 Rc   =  response  (area counts) for analyte in the cali-
                        bration standard.
15.5  Sample Analysis
     15.5.1  A 100  uL aliquot  of  the sample is drawn into a clean HPLC
             injection syringe.   The sample injection loop (10 uL) is
             loaded and  an  injection is  made.  The data system, if avai-
             ble, is  activated simultaneously with the injection and the
             point  of injection is  marked on  the strip-chart recorded.
     15.5.2  After  approximately  one minute,  the injection valve is
             returned to the "load" position  and the syringe and valve
             are flushed with  water in preparation for the next sample
             analysis.
     15.5.3  After  elution  of  the last component of interest, concen-
             trations are  calculated as  described in Section 16.2.3.
             [Note:  Table  8.0 illustrates typical retention times asso-
             ciates with individual PAHs, while Figure 17 represent a
             typical  chromatogram associates  with fluorescence detection.]
     15.5.4  After  the last compound of  interest has eluted, establish
             a stable baseline; the system can be now used for further
             sample analyses as described above.
     15.5.5  If the concentration of analyte  exceeds the linear  range
             of the instrument, the sample should be diluted with mobile
             phase, or a smaller  volume  can be injected into the HPLC.

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                                T013-57


      15.5.6  Calculate surrogate standard recovery on all  samples,  blanks

              and spikes.  Calculate the percent difference by  the  follow-
              ing equation:

                            % difference = SR-  ST  x 100
                                             Si

                Where

                     Sj  = surrogate  injected, ng.
                     SR  = surrogate  recovered,  ng.

      15.5.7  Once  a  minimum of  thirty  samples  of  the  same matrix have been

              analyzed,  calculte the  averge  percent  recovery (%R) and stand-

              ard deviation  of the percent  recovery  (SD) for the surrogate.

      15.5.8  For a given matrix, calculate  the  upper  and lower control

              limit for method performance  for the  surrogate standard.
              This  should be  done as  follows:

                   Upper  Control Limit  (UCL) =  (%R) +  3(SD)

                   Lower  Control Limit  (LCL) = (%R) -  3(SD)

              The surrogate  recovery must fall within  the control limits.

              If recovery  is  not within limits,  the following is required.

               o  Check  to be sure there are no errors in calculations
                   surrogate  solutions and internal standards.   Also,
                   check instrument performance.

               o  Recalculate the data and/or reanalyze the extract if
                  any of the above checks reveal a problem.

               o  Reextract  and  reanalyze the sample if none of the
                  above are  a problem or flag the data as  "estimated
                  concentration."

     15.5.9  Determine the concentration of each analyte in the sample

             according to Sections  17.1 and 17.2.3.

15.6  HPLC System Performance

     15.6.1  The general  appearance  of  the HPLC system should be

             similar  to  that illustrated in  Figure 10.

     15.6.2  HPLC  system efficiency  is  calculated  according to  the
             following equation:

                 N  *  5.54     t 2

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                              T013-58
              where:
                 N =  column  efficiency  (theoretical plates).
                tr =  retention time  (seconds)  of  analyte.
              wl/2 =  width of  component  peak at half  height
                     (seconds).
              A column  efficiency of >5,000 theoretical plates  should
              be obtained.
      15.6.3  Precision of response  for  replicate HPLC  injections  should
              be +10% or less, day to day, for analyte  calibration stand-
              ards at 1 ug/mL  or greater levels.   At  0.5 ug/mL  level and
              below,  precision of replicate analyses  could vary up to 25%.
              Precision of retention times should be  +2% on a given day.
      15.6.4  From the  calibration standards,  area responses for each
              PAH compound can be used against the concentrations  to
              establish working  calibration curves.   The calibration
              curve must be  linear and have a  correlation coefficient
              greater than 0.98  to be acceptable.
      15.6.5  The working calibration curve should be checked daily with
              an analysis of one or  more calibration  standards. If the
              observed  response  (rp) for any PAH  varies by more than 15%
              from the  predicted response (rp), the test method must be
              repeated  with  new calibration standards.  Alternately a new
              calibration curve  must be  prepared.  [Note: If rn -  Pp
              >15%, recalibration is necessary.]                Pp
15.7  HPLC Method Modification
      15.7.1  The HPLC  procedure has been automated by  Acurex Corpora-
              tion as part of  their  "Standard  Operating Procedure  for
              Polynuclear Aromatic Hydrocarbon Analysis by High Perform-
              ance Liquid Chromatography Methods," as reported  in  Refer-
              ence 9  of Section 18.
      15.7.2  The system consists of a  Spectra Physics  8100 Liquid Chpomat-
              ograph, a micro-processor-controlled HPLC, a ternary gradient
              generator, and an autosampler  (10 uL injection loop).
      15.7.3  The chromatographic analysis involves an  automated solvent
              program allowing unattended instrument  operation. The

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                        T013-59

        solvent program consists of four timed segments using
        varying concentrations of acetonitrile in water with a
        constant flow rate, a constant column temperature, and a
        10-minute equilibration time, as outlined below.
                    AUTOMATED HPLC WORKING PARAMETERS
                           Solvent
        Time             Composition       Temperature     Rate
        10 minutes      40% Acetonitrile   27.0 +_ 2°C    1 mL/min
        equilibration   60% Water
        T=0             40% Acetonitrile
                        60% Water
        T=25           100% Acetonitrile
        T=35           100% Acetonitrile
        T=45            40% Acetonitrile
                        60% Water
        Table 9.0 outlines the associated PAHs with their minimum
        detection limits (MDL) which can be detected employing
        the automated HPLC methodology.
15.7.4  A Vydac or equivalent analytical  column packed with a CIQ
        bonded phase is used for PAH separation with a reverse
        phase guard column.  The optical  detection system consists
        of a Spectra Physics 8440 variable Ultraviolet (UV)/Visible
        (VIS) wavelength detector and a  Perkin Elmer LS-4 Fluores-
        cence Spectrometer.  The UV/VIS  detector, controlled by
        remote programmed commands, contains a Deuterium lamp with
        wavelength selection between 150 and 600 nanometers.  It
        is set at 254 nanometers with the time constant (detector
        response) at 1.0 seconds.
15.7.5  The LS-4 Fluorescence Spectrometer contains separate exci-
        tation and  emission monochromators which are positioned
        by separate microprocessor-controlled stepper motors.  It
        contains a Xenon discharge lamp,  side-on photomultiplier
        and a 3-microliter illuminated volume flow cell.  It is
        equipped with a wavelength programming facility to set
        the monochromators automatically to a given wavelength
        position.  This greatly enhances  selectivity by changing

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                                 T013-60
                 the fluorescence excitation and emission detection wave-
                 lengths during the chromatographic separation in order to
                 optimize the detection of each PAH.  The excitation wave-
                 lengths range from 230 to 720 nanometers; the emission
                 wavelengths range from 250 to 800 nanometes.  The excita-
                 tion and emission slits are both set at 10 nanometers
                 nominal bandpass.
          15.7.6  The UV detector is used for determining naphthalene, acenap-
                 thylene and acenapthene, and the fluorescence detector is
                 used for the remaining PAHs.  Table 9 outlines the detec-
                 tion techniques and minimum detection limit (MDL) employing
                 this HPLC system.  A Dual Channel Spectra Physics (SP) 4200
                 computing integrator, with a Labnet power supply, provides
                 data analysis and a chromatogram.  An IBM PC XT with a
                 10-megabyte hard disk provides data storage and reporting.
                 Both the SP4200 and the  IBM PC XT can control all functions
                 of the instruments in the series through the Labnet system
                 except for the LS-4, whose wavelength program is  started
                 with a signal from the High Performance  Liquid Chromatograph
                 autosampler when it injects.  All data  are  transmitted to
                 the XT and stored on the hard disk.  Data files  can later
                 be transmitted to floppy disk  storage.
16.0 Quality Assurance/Quality Control
     16.1 General System QA/QC
          16.1.1 Each laboratory that  uses  these  methods  is  required to oper-
                 ate  a  formal quality  control  program.   The  minimum require-
                 ments  of  this  program consist  of an initial  demonstration
                  of laboratory  capability and  an  ongoing analysis of  spiked
                  samples  to  evaluate  and  document quality data.   The  labora-
                  tory must maintain  records  to  document  the  quality of the
                  data generated.   Ongoing data quality  checks are compared
                  with established  performance  criteria  to determine if the
                  results of analyses  meet the  performance characteristics of
                  the method.   When  results of  sample spikes  indicate a
                  typical  method performance, a quality  control  check stand-
                  ard must be analyzed to confirm that the measurements were
                  performed in an in-control mode of operation.

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                               T013-61

       16.1.2  Before  processing any  samples, the analyst should demon-
              strate, through the analysis of a reagent solvent blank,
              that  interferences from the analytical system, glassware,
              and reagents are  under control.  Each time a set of samples
              is extracted or there  is a change in  reagents, a reagent
              solvent blank should be processed as a safeguard against
              chronic laboratory contamination.  The blank samples should
              be carried through all stages of the sample preparation
              and measurement steps.
       16.1.3  For each analytical  batch (up to 20 samples), a reagent
              blank, matrix spike and deuterated/surrogate samples must •
              be analyzed (the frequency of the spikes may be different
              for different monitoring programs).  The blank and  spiked
              samples must be carried through all stages of the sample
              preparation and measurement steps.
       16.1.4  The experience of the analyst performing gas chromatography
              and high performance liquid chromatography is invaluable
              to the success of the methods.   Each day that analysis  is
              performed, the daily calibration sample should be evaluated
             to determine if the  chromatographic system is operating
             properly.   Questions  that should be asked are:   Do  the
              peaks look normal?;  Is  the  response windows  obtained
             comparable to  the response  from previous calibrations?
             Careful  examination  of  the  standard chromatogram can
             indicate whether the  column  is  still  good, the  injector is
             leaking, the injector  septum needs  replacing,  etc.   If  any
             changes  are made.to the system  (e.g.,  column  changed),
             recalibration  of  the  system  must  take  place.
16.2  Process, Field, and Solvent Blanks
      16.2.1  One cartridge  (XAD-2 or PUF)  and  filter from each batch  of
             approximately twenty should  be  analyzed,  without  shipment
             to  the field, for  the compounds of  interest per  to serve  as
             a process blank.   A blank level of  less  than 10  ng per
             cartridge/filter  assembly for single PAH  component is
             considered  to be acceptable.

-------
                             TO13-62
      16.2.2   During  each  sampling episode, at least one cartridge and
              filter  should  be shipped to the field and returned, without
              drawing air  through the sampler, to serve as a field blank.
      16.2.3   During  the analysis of each batch of samples at least one
              solvent process blank  (all steps conducted but no cartridge
              or filter included) should be carried through the procedure
              and analyzed.  Blank levels should be less than 10 ng/sample
              for single components  to be acceptable.
      16.2.4   Because the  sampling configuration (filter and backup
              adsorbent) has been tested for targeted PAHs in the
              laboratory in  relationship to collection efficiency and
              has been demonstrated  to be greater than 95% for targeted
              PAHs, no field recovery evaluation will occur as part of
              the QA/QC program outlined in this section.
16.3  Gas Chromatography with Flame  lonization Detection
      16.3.1   Under the calibration  procedures (internal and external), the
              % RSD of the calibration factor should be <20% over the
              linear  working range of a  five point calibration curve
              (Sections 13.4.1.6 and 13.4.2.6).
      16.3.2   Under the calibration  procedures (internal and external),
              the daily working calibration curve for each analyte should
              not vary from  the predicted  response by more than +20%
              (Sections 13.4.1.7 and 13.4.2.8).
      16.3.3   For each analyte, the  retention time window must be
              established  (Section 13.5.1), verified on a daily  basis
              (Section 13.6.3.2)  and established for each analyte
              throughout the course  of  a 72-hour period (Section 13.5.3).
      16.3.4   For each analyte, the  mid-level standard must  fall within  the
              retention time window  on  a daily basis as a qualitative
              performance  evaluation of  the GC system  (Section 13.6.3.4).
      16.3.5   The surrogate  standard recovery must not deviate  from  100%
              by no more  than  20%  (Section  13.6.3.5).

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                              T013-63

16.4  Gas Chromatography with Mass  Spectroscopy  Detection
      16.4.1   Section  14.5.1  requires  the mass spectrometer be tuned
              daily  with DFTPP and  meet  relative  ion  abundance require-
              ments  outlined  in Table  3.
      16.4.2   Section  14.3.1.1 requires  a minimum of  five concentration
              levels of  each  analyte  (plus deuterated internal standards)
              be  prepared to  establish a calibration  factor to illustrate
              <20% variance over the linear working range of the
              calibration curve.
      16.4.3   Section  14.3.1.13 requires the verification of the working
              curve  each working  day (if using the external standard tech-
              nique) by  the measurement of one or more calibration stand-
              ards.  The predicted  response must  not vary by more than
              +20%.
      16.4.4   Section  14.3.2.6  requires the initial calibration curve
              be  verified each  working day (if using the internal standard
              technique)  by the measurement of one or more calibration
              standards.   If the  response varies by more than +20% of
              predicted  response, a fresh calibration curve (five point)
              must be  established.
      16.4.5   Section  14.4.5 requires that for sample analysis, the com-
              parison  between the sample and reference spectrum illustrate:
              (1)  Relative intensities of major ions in the reference
              spectrum (ions >10% of the most abundant ion) should be
              present  in the sample spectrum.
              (2)  The relative intensities  of the major ions  should
              agree within +20%.  (Example:   For an ion with an abundance
              of 50% in the standard spectrum, the corresponding  sample
              ion abundance must be between  30 and 70%).
              (3)  Molecular ions present in the  reference spectrum
             should  be present in sample the  spectrum.
              (4)  Ions present in the sample  spectrum but not  in the
             reference spectrum should be  reviewed for possible  back-
             ground  contaminatiuon or presence  of coeluting  compounds.
             (5)   Ions present in the  reference  spectrum but  not in
             the sample  spectrum should  be  reviewed  for possible sub-
             traction  from the sample  spectrum  because  of background
             contamination or coeluting  peaks.   Data  system  library  re-
             duction programs can sometimes create these discrepancies.

-------
                                 T013-64
         16.4.6  Section 14.5.3 requires that initial calibration curve be
                 verified every twelve continuous hour of analysis by a
                 mid-level calibration standard.  The response must be
                 less than 20% difference from the initial response.
         16.4.7  The surrogate standard recovery must not deviate from 100%
                 by no more than 20% (Section 14.5.4).
    16.5  High Performance Liquid Chromatography
         16.5.1  Section 15.4.4 requires the preparation of calibration
                 standards at a minimum of five concentration levels to
                 establish correlation coefficient of at least 0.999 for a
                 linear least-squares fit of the data.
         16.5.2  Section 15.4.5 requires that the retention time for each
                 analyte should agree within +2%.
         16.5.3  A daily calibration check involving an  intermediate
                 standard of the initial five point  calibration curve
                 should be within +15% from day to day.
         16.5.4  Section  15.5.6 requires the calculation of percent difference
                 of  surrogate standard recovery in order to establish
                 control  limits:
                 Upper Control Limit  (UCL) = (%R) +  3 (SD)
                 Lower Control Limit  (LCL) = (%R) -  3 (SD)
                 The  surrogate recovery must fall within the  control  limits.
17.   Calculations
     17.1  Sample Volume
         17.1.1  The  total sample volume  should  be corrected  to  standard
                 temperature  and  pressure.
          17.1.2  The  total sample volume  (Vm)  is  calculated from the
                  periodic flow readings  (Magnehelic  readings  taken  in
                  Section  11.3.13) using the  following equation.
                               Vm = Qi  +  Q?  ...On x   T
                                          N           1000
                     Where
                               Vm = total  sample volume (m3)  at  ambient
                                     conditions  .
                       Ql, Q2-..Qn = flow rates  determined at  the beginning,
                                     end,  and intermediate points during
                                     sampling (m3/minute).
                                 N = number of data points.
                                 T = elapsed  sampling time (minutes).

-------
                        T013-65
17.1.3  The volume of air sampled  can  be  converted to standard

        conditions (760 mm Hg pressure and  25°C)  using the

        following equation:
                      Vc = Vm x Pfl  x 298
           Where
                                     760   273 + tA
                                                      o
                            V_ = total sample volume (m) at standard
                                temperature and pressure (25°C and 760 mm
                                Hg  pressure).

                            Vm = total sample flow under ambient conditions
                                (m3).

                            PA = ambient pressure (mm Hg).

                            tA = ambient temperature (°C).

17.2  Sample Concentration

      17.2.1  6C/FI  Detection

              17.2.1.1   The  concentration  of each analyte in the sample
                        may  be determined from the external standard tech-

                        nique  by calculating the amount of standard

                        injected,  from the peak response, using the

                        calibration  curve  or the calibration factor

                        determined in Section 13.4.1.6.

              17.2.1.2   The  concentration  of a specific analyte is

                        calculated as follows:

                          Concentration, ng/m3 = C(Aj(Vt)(D)3

                        Where:

                              CF = calibration factor for chromatographic
                                  system, peak height or area response
                                  per mass injected, Section 13.4.1.6.

                              Ax = Response for the analyte in the
                                  sample, area counts or peak height.

                              Vt = volume  of total sample, uL.

                              D  = Dilution factor, if dilution was made
                                  on the  sample prior to analysis.   If
                                  no dilution was made, D=l, dimensionless.

                              Vi = volume  of sample injected, uL
                                                        o
                              V  = total  sample volume  (m ) at standard
                                  temperature and  pressure (25°C  and
                                   760  mm Hg), Section 17.1.3.

-------
                        T013-66

 17.2.2   GC/MS Detection
         17.2.2.1  When an analyte has been identified, the quanti-
                  fication of that analyte will be based on the
                  integrated abundance from the monitoring of the
                  primary characteristic ion.  Quantification will
                  take place using the internal standard technique.
                  The internal standard used shall be the one
                  nearest the retention time of that of a given
                  analyte (see Section 14.3.2.1).
         17.2.2.2  Calculate the concentration of each identified
                  analyte in the sample as follows:
                    Concentration, ng/m3 = [(AV)(IC)(V^.)(D)]
                                           b \  X ' > i 5 n ' t' >u •' J
                                           L(A{S)(RFJ(VI)(VS)]
                    Where
                         Ax = area of characteristic ion(s)
                              for analyte being measured.
                         Is = amount of internal  standard
                              injected, ng.
                         Vt - volume of total  sample,  uL.
                         D  = dilution factor, if dilution was
                              made on the sample  prior  to  analysis.
                              If no dilution was  made,  D  = 1,
                              dimensionless.
                        AJS = area of characteristic ion(s)  for
                              internal  standard.
                         RF = Response factor  for  analyte  being
                              measured, Section 14.3.2.5.
                         Vj = volume of analyte injected,  uL.
                         Vs = total  sample volume  (m3)  at  standard
                              temperature  and  pressure  (25°C  and
                              760  mm Hg),  Section  17.1.3.
17.2.3  HPLC Detection
        17.2.3.1   The concentration  of  each  analyte  in  the
                  sample may be  determined  from the  external
                  standard  technique by calculating  response
                  factor and peak  response  using the calibration
                  curve.

-------
                             T013-67


             17.2.3.2  The concentration of  a specific  analyte  is
                       calculated  as  follows:

                         Concentration, ng/m3 = FfRF  )(A

                         Where
                             RFC = response factor (nanograms injected
                                   per area counts) calculated in
                                   Section 15.4.7.

                              Ax » response for the analyte in the sample,
                                   area counts or peak height.

                              Vt = volume of total sample, uL.

                              D  = dilution factor, if dilution was
                                   made on the sample prior to analysis.
                                   If no dilution was made, D = 1,
                                   dimensionless.

                              Vi = volume of sample injected, uL.
                                                         o
                              V  » total sample volume  (nr)  at standard
                                   temperature and pressure  (25°C and
                                   760 mm Hg), Section  17.1.3.

17.3  Sample Concentration Conversion From ng/m3 to ppbv

      17.3.1  The concentrations  calculated  in  Section 17.2 can be
              converted to ppbv  for  general  reference.
      17.3.2  The analyte concentration  can  be  converted  to ppbv  using

              the following equation:

                C« (ppbv) - C« (ng/m3)  x 24.4
                 A           A           MWA

                Where

                      C« - concentration of analyte, ng/m , calculated
                           according to Sections  17.2.1  through 17.2.3.

                     MWA = molecular weight of analyte,  g/g-mole

                    24.4 = molar volume occupied by ideal gas at
                           standard temperature and pressure (25°C and
                           760 mm Hg), I/mole.

-------
                              T013-68
                          18.0  BIBLIOGRAPHY

 1.   Dubois,  L.,  Zdrojgwski, A., Baker, C., and Monknao J.L., "Some Improve-
     ment  in  the  Determination of Benzo[a]Pyrene in Air Samples," Air Pol-
     lution Control Association J., 17:818-821, 1967.
 2.   Intersociety Committee "Tentative Method of Analysis for Polynuclear
     Aromantic  Hydrocarbon of Atmospheric Particulate Matter, Health Labora-
     tory  Science, Vol. 7, No. 1, pp. 31-40, January, 1970.
 3.   Cautreels, W., and Van Cauwenberghe, K., "Experiments on the Distribu-
     tion  of  Organic  Pollutants Between Airborne Particulate Matter and
     Corresponding Gas Phase", Atmos. Environ., 12:1133-1141 (1978).
 4.   "Tentative Method of Microanalysis for Benzo[a]Pyrene in Airborne
     Particules and Source Effluents," American Public Health Association,
     Health Laboratory Science, Vol 7, No. 1, pp. 56-59, January, 1970.
 5.   "Tentative Method of Chromatographic Analysis for Benzo[a]Pyrene and
     Benzo[k]Fluoranthene in Atmospheric Particulate Matter," American
     Public Health Association, Health Laboratory Science, Vol. 7, No. 1,
     pp. 60-67, January, 1970.
 6.   "Tentative Method of Spectrophotometric Analysis for Benzo[a]Pyrene
     in Atmospheric Particulate Matter," American Public Health Association,
     Health Laboratory Science, Vol. 7, No. 1, pp. 68-71, January, 1970.
 7.   Jones, P.M., Wilkinson, J.E., and Strup, P.E., "Measurement of Poly-
     cyclic Organic Materials and Other Hazardous Organic Compounds in
     Stack Gases: State-of-art," U.S. EPA-600/2-77-202, 1977.
 8.   "Standard  Operating Procedure for Ultrasonic Extraction and Analysis
     of Residual  Benzo[a]Pyrene from Hi-Vol Filters via Thin-Layer Chroma-
     tography", J.F.  Walling, U.S. Environmental Protection Agency, Environ-
     mental Monitoring Systems Laboratory, Methods Development and Analysis
     Division,  Research Triangle Park, N.C., EMSL/RTP-SOP-MDAD-015, December,
     1986.
 9.   "Standard  Operating Procedure for Polynuclear Aromantic Hydrocarbon
     Analysis by  High Performance Liquid Chromatography Methods," Susan Rasor,
     Acurex Corporation, Research Triangle Park, N.C., 1978.
10.   Rapport, S.W., Wang,  Y.Y., Wei, E.T., Sawyer, R., Watkins, B.E., and
     Rapport, H., "Isolation and Identification of a Direct-Acting Mutagen
     in Diesel  Exhaust Particulates", Envir. Sci. Technol., 14:1505-1509,
     1980.

-------
                               T013-69
11.  Konlg,  J., Balfanz,  E.,  Funcke, W., and Romanowski, T., "Determination
     of Oxygenated Polycyclic Aromantic Hydorcarbons in Airborne Particu-
     late Matter by Capillary Gas Chromatography and Gas Chromatography/Mass
     Spectrometry",  Anal.  Chem., Vol. 55, pp. 599-603, 1983.
12.  Chuang, J. C., Bresler,W. E. and Hannan, S. W.."Evaluation of Polyurethane
     Foam Cartridges for  Measurement of Polynuclear Aromantic Hydrocarbons
     in Air," U.S. Environmental Protection Agency, Environmental Monitoring
     Systems Laboratory,  Methods Development and Analysis Division, Research
     Triangle Park, N.C., EPA-600/4-85-055, September,  1985.
13.  Chuang, J.C., Hannan, S.W., and Kogtz, J. R.,  "Stability of Polynuclear
     Aromantic Compounds  Collected  from Air on Quartz Fiber Filters and XAD-2
     Resin," U.S. Environmental Protection Agency,  Environmental Monitoring
     Systems Laboratory,  Methods Development and Analysis Division, Research
     Triangle Park, N.C., EPA-600/4-86-029, September,  1986.
14.  Feng, Y. and Bidleman, T.F., "Influence of Volatility on the Collection
     of Polynuclear Aromantic Hydrocarbon Vapors with Polyurethane Foam",
     Envir.  Sci. Technol., 18:330-333, 1984.
15.  Yamasaki, H., Kuwata, K., and  Miyamoto, H., "Effects of Ambient Tempera-
     ture on Aspects of Airborne Polycyclic Aromantic Hydrocarbons", Envir.
     Sci. Technol., Vol.  16,  pp. 189-194, 1982.
16.  Chuang, J.C., Hannan, S.W. and Kogtz, J. R.,  "Comparison of Polyurethane
     Foam and XAD-2 Resin as  Collection Media for  Polynuclear Aromantic
     Hydrocarbons in Air," U.S. Environmental Protection Agency, Environmental
     Monitoring Systems Laboratory, Methods Development and Analysis Division,
     Research Triangle Park,  N.C.,  EPA-600/4-86-034, December,  1986.
17.  Chuang, J. C., Mack, G.  A., Mondron, P. J.  and Peterson,  B. A.,  "Evalua-
     ation of Sampling and Analyjtical Methodology for  Polynuclear Aromatic
     Compounds in Indoor  Air," Environmental Protection Agency, Environmental,
     Monitoring Systems Laboratory, Methods Development and Analysis Division,
     Research Triangle Park,  N.C.,  EPA-600/4-85-065, January, 1986.
18.  Methods for Organic  Chemical Analysis of Municipal and  Industrial Waste-
     water,  U.S. Environmental Protection Agency,  Environmental  Monitoring
     and Support Laboratory,  Cincinnati, OH, EPA-600/4-82-057,  July 1982.
19.  ASTM Annual Book of  Standards, Part 31, D 3694.   "Standard Practice  for
     Preparation of Sample Containers  and for Preservation," American  Society
     fdr Testing and Materials, Philadelphia, PA,  p. 679,  1980.

-------
                               T013-70
20.  Burke, J.A., "Gas Chromatography for  Pesticle  Residue Analysis; Some
     Practical  Aspects," Journal  of  the  Association  of Official Analytical
     Chemists,  Vol.  48, p.  1037,  1965.
21.  Cole, T.,  Riggins, R., and Glaser,  J.,  "Evaculation of Method Detection
     Limits an  Analytical  Curve for  EPA  Merhod  610  - PNAs," International
     Symposium  on Polynuclear Aromantic  Hydrocarbons, 5th, Battelle Columbus
     Laboratory, Columbus,  Ohio,  1980.
22.  "Handbook  of Analytical  Quality Control  in Water and Wastewater Labora-
     tories, "U.S. Environmental  Protection  Agency,  Environmental Monitoring
     and Support Laboratory,  Cincinnati, Ohio 45268, EPA-600/4-79-019, March,
     1979.
23.  ASTM Annual Book of Standards,  Part 31,  D  3370, "Standard Practice  for
     Sampling Water," American Society for Testing  and Materials, Philadelphia
     PA, p. 76, 1980.
24.  Protocol for the Collection and Analysis of  Volatile POHC's  (Principal
     Organic Hazardous Constituents) using VOST (Volatile Organic Sampling
     Train), PB84-170042,  EPA-600/8-84-007,  March,  1984.
25.  Sampling and Analysis Methods for Hazardous  Waste Combustion - Methods
     3500, 3540, 3610, 3630,  8100, 8270, and  8310;  Test Methods For Evaluating
     Solid Waste (SW-846),  U.S. EPA, Office  of  Solid Waste, Washington,  D.C.
26.  Chuang, C.C. and Peterson, B.A.,  "Review of  Sampling and Analysis Method-
     ology for  Polunuclear Aromantic Compounds  in Air from Mobile Sources",
     Final Report, EPA-600/S4-85-045, August, 1985.
27.  "Measurement of Polycyclic Organic  Matter  for  Environmental Assessment,"
     U.S. Environmental Protection Agency, Industrial Environmental Research
     Laboratory, Research Triangle Park, N.C.,  EPA-600/7-79-191, August, 1979.
28.  "Standard  Operating Procedure No. FA  113C:  Monitoring For Particulate
     and Vapor  Phase Pollutants Using the  Portable  Particulate/Vapor Air
     Sampler,"  J.L. Hudson, U.S. Environmental  Protection Agency, Region VII,
     Environmental Monitoring and Compliance Branch, Environmental  Services
     Division,  Kansas City, Kansas,  March, 1987.
29.  Technical  Assistance Document  for  Sampling and Analysis  of Toxic  Organic
     Compounds  in Ambient Air, U.S.  Environmental Protection  Agency, Environ-
     mental Monitoring Systems Laboratory, Quality  Assurance  Division,
     Research Triangle Park,  N.C., EPA-600/4-83-027, June,  1983.

-------
                                  T013-71

30.  Winberry,  W. T.,  Murphy,  N.T.,  Supplement  to Compendium of Methods
     for the Determination  of  Toxic  Organic  Compounds in Ambient Air,
     U.S. Environmental  Protection Agency, Environmental Monitoring Systems
     Laboratory, Quality Assurance Division, Research Triangle Park, N.C.,
     EPA-600/4-87-006, September, 1986.
31.  Riggins, R. M., Compendium of Methods  for  the  Determination of Toxic
     Organic Compounds in Ambient Air, U.S.  Environmental  Protection
     Agency, Environmental  Monitoring Systems Laboratory,  Quality Assurance
     Division Research Triangle Park, N.C.,  EPA-600/4-84-041, April, 1984.
32.  Quality Assurance Handbook for  Air Pollution Measurement Systems,  Vo-
     lume II - "Ambient Air Specific Methods,"  Section  2.2 -  "Reference
     Method for the Determination of Suspended Particulates in the Atmos-
     phere," Revision 1, July, 1979, EPA-600/4-77-027A.
33.  ASTM Annual Book of Standards,  Part 31, D 3694.  "Standard  Practice
     for Preparation of Sample Containers and for Preservation," American
     Society for Testing and Materials, Philadelphia,  PA,  p.  679,  1980.   '
34.  "HPLC Troubleshooting Guide - How to Identify, Isolate,  and Correct  '*
     Many HPLC Problems," Supelco, Inc., Supelco Park,  Bellefonte,  PA,
     16823-0048, Guide 826, 1986.
35.  "Carcinogens - Working With Carcinogens," Department  of Health,
     Education,  and Welfare,  Public Health Service, Center for Disease
     Control, National  Institute for Occupational  Safety and Health,
     Publication  No. 77-206,  August, 1977.
36.  "OSHA  Safety and Health  Standards, General Industry," (29CFR1910),
     Occupational Safety and  Health Administration, OSHA 2206, Revised,
     January, 1976.
37.  "Safety in  Academic Chemistry  Laboratories,'1 American Chemical  Society
     Publication, Committee on Chemical Safety, 3rd Edition, 1979.
38.  Hudson, J., "Monitoring  for Particulate And Vapor Phase Pollutants
     Using  A Portable Particulate/Vapor Air  Sampler -  Standard Operating
     Procedure  No.  SA-113-C", U.S.  Environmental Protection Agency, Region
     VII, Environmental  Services  Division,  25  Funston  Road, Kansas City,
     Kansas, 66115.

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                                           T013-72
              TABLE 1.0   FORMULAE AND  PHYSICAL PROPERTIES OF SELECTIVE PAHs

Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b) f 1 uoranthene
Benzo(e)pyrene
Benzo(g.h,i)perlene
Benzo(k)fl uoranthene
Chrysene
Dibenzo(a,h)anthracene
Fl uoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
^Naphthalene
Phenanthrene
Pyrene
FORMULA
C12H10
C12H8
Ci4Hio
C18H12
C20H12
C20H12
C2QH12
C22H12
C20Hi2
Cl8Hl2
C£2Hi4
c^io
Cl3HlO
C22H12
ClOHs
Ci4Hio
CieHio
MOLECULAR
WEIGHT
154.21
152.20
178.22
228.29
252.32
252.32
252.32
276.34
252.32
228.29
278.35
202.26
166.22
276.34
128.16
178.22
202.26
MELTING POINT
°C
96.2°
92-93
218°
158-159
177°
168
178-179
273
217
255-256
262
110
116-117
161.5-163
80.2
100°
156
BOILING POINT
°C
279
265-275
342
-
310-312
_
-
480
-
-
-
293-295
-
217.9
340
399
CASE
#
83-32-9
208-96-8
120-12-7
56-55-3
50-32-8
205-99-2
192-92-2
191-24-2
207-08-9
218-01-9
53-70-3
206-44-0
86-73-7
193-39-5
91-20-3
85-01-8
129-00-0
*Many of these compounds  sublime.
            recycled paper
                                                                   ecology and environment

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                               T013-73


        TABLE 2.0  RETENTION TIMES  FOR SELECTIVE PAHs FOR PACKED
                         AND CAPILLARY COLUMNS
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(ghi)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo( a, h) anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
10.8
1 f\ A
10.4
1C f\
15,9
20.6
29.4
28.0
38.6
28.0
f\ A T
24.7
36.2
19.8
12.6
36.2
4.5
1C rt
15.9
20.6
                              Packed1	Capillary2
                                                     16.8
                                                     15.9
                                                     20.7
                                                     29.1
                                                     36.2
                                                     34.2
                                                     48.4
                                                     34.4
                                                     29.3
                                                     46.1
                                                     24.3
                                                     18.1
                                                     45.6
                                                     11.0
                                                     20.6
                                                     25.0
    conditions:   Chromosorb  W-AW-DMCS  (100/120 mesh) coated with 3%
 OV-17,  packed  in a 1.8-m long  x  2 mm  ID glass column, with nitrogen
 carrier gas at a flow rate  of  40 mL/min.  Column temperature was held
 at 100°C for 4 min. then programmed at 8°/minute to a final hold at 280 C.

2Capillary GC conditions: 30 meter fused  silica SPB-5 capillary column;
 flame ionization detector,  splitless  injection; oven temperature held at
 80 Segree  C for 2 minutes, increased at  8  degrees/min. to 280 degrees C.

-------
                                T013-74
          TABLE  3.0  DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
  Mass
  68
  70

 127

 197
 198
 199

 275

 365

441
442
443
    Ion Abundance Criteria
    —•	—-—
 30-60% of mass 198

 Less  than 2%  of  mass 69
 Less  than 2%  of  mass 69

 40-60% of mass 198

 Less  than 1%  of  mass  198
 Base  peak,  100%  relative  abundance
 5-9%  of mass  198

 10-30% of mass 198

Greater than 1% of mass 198

Present but less  than mass 443
Greater than 40%  of mass 198
17-23% of mass 442

-------
                                T013-75


                TABLE  4.0   GC  AND  MS  OPERATING  CONDITIONS
Chromatography

folumn                     Hewlett-Packard Ultra #2  crossi inked  5%  phenyl
 °                         methyl silicone (50 m x 0.25 mm,  0.25 urn film
                           thickness)  or equivalent

Carrier Gas                Helium velocity 20 cm3/sec at 250°C
Injection Volume           Constant (1-3 uL)
Injection Mode             Splitless

Temperature Program

Initial Column Temperature 45°C

                           i^to 100°C  in 5 rcin, then 100°C to 320«C at
                           8°C/min
Final  Hold Time            15 min

Mass  Spectrometer

Detection  Mode             Multiple ion detection, SIM mode

-------
                                  T013-76
  j-naphthalene
 Dio-phenanthrene
 Phenathrene
 Anthracene
 Fluoranthene
 D10-Pyrene
 Pyrene
 Cyclopenta[c,d]pyrene
 Benz[a]anthracene
Di2-chrysene
Benzo[e]pyrene
Di2-benzo[a]pyrene
Benzo[a]pyrene
 136
 188
 178
 178
 202
 212
 202
 226
 228
240
252
264
252

-------
                                T013-77
          TABLE  6.0  CHARACTERISTIC  IONS  FROM GC/MS  DETECTION
                           FOR SELECTED PAHs
                                  Primary
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(ghi)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
154
152
178
228
252
252
276
252
228
278
202
166
276
128
178
202
153
151
179
229
253
253
138
253
226
139
101
165
138
129
179
200
Secondajx

 152
 153
 176
 226
 125
 125
 277
 125
 229
 279
 203
 167
 227
 127
 176
 203

-------
                                 T013-78
             TABLE 7.0.  COMMERCIAL AVAILABLE COLUMNS FOR PAH
                           ANALYSIS USING HPLC
  Company
Column Identification
Column Name
The Separation Group
P.O. Box 867
Hesperia, California 92345

Rainin Instrument Company
Mack Road
Wasurn, MA 01801-4626

Supelco, Inc.
Supelco Park
Bellefonte, PA 16823-0048

DuPont Company
Biotechnology Systems
Barley Mill Plaza, P24
Wilmington, DE 19898

Perkin-Elmer Corp.
Corporate Office
Main Avenue
Norwalk, CT 06856

Waters Associates
34-T Maple St.
Mil ford, MA 01757
        201-TP
    Ultrasphere - ODS
        LC-PAH
        ODS
  VYDAC
  ALEX
  Supelcosil
  Zorbax
        HC-ODS
       u-Bondapak
  Sil-X
  NH3 u-Bondapak

-------
                                T013-79





        TABLE 8.0.  TYPICAL RETENTION TIME FOR SELECTIVE  PAHs

                   BY  HPLC SEPARATION AND DETECTION
. — 	 	 	 	 ' 	 • 	
Compound



	 	 	

Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
tenzo(a)pyrene
Benzo(b)fluoranthene
3enzo(e)pyrene
Benzo(ghi)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
__ — 	 	 	 	 • 	 ! 	
	 	 	 	 — 	 	 —
Retention Times (minutes)
HPLC Conditions 	
Condition A
Fluorescence UV
	 	 	 	 	 — ' — • —
20 5
tw • */
18 5
•LV-' • v
00 A
£J.£T
oo c
28.5
OO Q
oo.y
31.6
36.3
32.9
9Q "?
U3 . *^
35.7
*)A C
£H.3
21.2
37.4
16 6
xu . u
OO 1
C.C.,1
05 4
C. 
-------
                                 T013-80
TABLE 9.0.
               RETENTION TIMES (RT) AND MINIMUM DETECTION LIMITS (MDLs)  FOR
               SELECTED PAHs USING ULTRAVIOLET AND FLOURESCENCE  DETECTION
    PAH
                            Ultraviolet Detector

                             RT        MDL
RT = Retention time in minutes
MDL = Minimum detection limit
Flourescence Detector

   RT          MDL
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo{k)fluoranthene
Benzo(a)pyrene
Dibenzo(a,h)anthracene
Benzo(ghi)perylene
Indeno(1.2,3-cd)Dvrene
14.0
15.85
18.0
18.5
19.9
21.0
22.5
23.4
26.3
26.7
29.3
30.2
31.1
32.7
33.9
34.6
250pg/uL
250pg/uL
250pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
50pg/uL
18.5
19.9
21.0
22.5
23.4
26.3
26.7
29.3
30.2
31.1
32.7
33.9
34.6
                                                                     5pg/uL
                                                                    lOpg/uL
                                                                    50pg/uL
                                                                    lOpg/uL
                                                                     5pg/uL
                                                                     5pg/uL
                                                                     5pg/uL
                                                                    lOpg/uL
                                                                     5pg/uL
                                                                     5pg/uL
                                                                     5pg/uL
                                                                     5pg/uL
                                                                    50pg/uL

-------
                                     TO13-81
Acenaphthene
  Benzo(a)anthracene
 Benzo(g,h,!)perylene
       Chrysene
      Fluorene
  Acenaphthylene
Benzo(b)fluoranthene
   Benzo(a)pyrene
    Dibenz(a,h)anthracene
   lndeno(1,2,3-c,d)pyrene
                                                               Anthracene
                                                          Benzo(k)fluoranthene
                                                              Benzo(e)pyrene
                                                                  Fluoranthene
                                                                   Naphthalene
   Phenanthrene                           Pyrene




       FIGURE  1.0  RING STRUCTURE OF SELECTIVE PAHs.

-------
                                    TO 13-82
                                                    Filter Retaining Ring

                                                    Silicone Gasket
    Air Flow
           4" Diameter
           Pallflex  Filter
Particulate
Filter
Support
Adsorbent
Cartridge  and
Support
   Air Flow
   Exhaust
                                      4" Diameter
                                     -Pallflex
                                      Filter
                                      TX40H120WW
                                                    Filter Support Screen
                                                    Filter Support  Base
                                                    Silicone  Gasket
                                                    Glass Cartridge


                                                     Adsorbent
                                                    (XAD-2 or PUF)


                                                    Retaining  Screen
                                                   Silicone Gasket
                                                   Adsorbent
                                                   Support
FIGURE  2.0  GENERAL METAL WORKS SAMPLING HEAD

-------
                                       T013-83
Water In-
    Soxhlet
  Extraction.
  Tube and
    Thimble
                  $>-*• Water Out
                         Alllhn
                         Condenser
                         •Flask
       (a) Soxhlet Extraction Apparatus
           with AHihn Condenser
              3 Ball Macro
              Synder Column
                                                                   500 mL
                                                                   Evaporator
                                                                   Flask
                10 mL
                Concentrator
                Tube
(b) Kudema-Danish (K-D) Evaporator
    with Macro Synder Column
                  Disposable 6 inch
                  Pasteur Pipette
                                               -1 Gram Sodium Sulfate
                                               JO Gram Silica
                                               ~Gel Slurry
                                            -—Glass Wool Plug
                               (c) Silica Gel Clean-up Column
           FIGURE 3.  APPARATUS USES  IN SAMPLING ANALYSIS.

-------
        1ttaiuuo,nAira pus A'
                                   TO13-84
                   Sampling
                    Head
                 (See Figure 2)
  Magnehelic
   Gauge
  0-100 In.
                                                            Elapsed Time
                                                               Meter
 Exhaust
  Duct
(6 In. x 10 ft)
                               Base Plate
        FIGURE 4.   MODIFIED HIGH VOLUME  AIR SAMPLER

            GENERAL METAL WORKS MODEL PS-1 SAMPLER

-------
                                    TO13-85
Exhaust Hose
                                                    4" Diameter Pullflex
                                                    Filter And Support
                                                    XAD-2 or PUF Adsorbent
                                                    Cartridge And Support
                                                    Quick Release Connections
                                                    For Module
                                                    Quick Release Connections
                                                    For Magnahelic Gage
                                                    Flow Control Valve
                                                        Elapsed Time Indicator
       FIGURE  5.   PORTABLE HIGH VOLUME AIR SAMPLER

-------
                                  TO13-86
Mercury
Manometer
                                              Orifice
Barometer
                                                        Thermometer
                                                    Filter Adapter
                                                   Rootsmeter
                                                 High Volume Motor
       Resistance  Plates
  FIGURE 6.   LABORATORY ORIFICE CALIBRATION SETUP

-------
    '1

   PI
                  JC.
   Orifice No..
                K
             .mmHg
   Roots Meter No..
Name.


Date-
Resistance
Plates
(No. of Holes)
5
7
10
13
18
Air Volume
Measured By
Rootsmeter
Vm
(ft3)
200
200
300
300
300
(m3)
5.66
5.66
8.50
8.50
8.50
Standard
Volume
VSW
(std m3)





Time For Air
Volume To
Pass Through
Rootsmeter
0
(min)





Roots Meter
Pressure
Differential
AP
(mm Hg)





Pressure
Drop Across
Orifice
AH
(in.H2O)





x-Axis
Standard
Flow Rate
Qstd
(std m3/min)





y-Axis
VAH(P1/Psfd)(298/T1)
Value





                                                                                                     GO


                                                                                                     OO
Factors: (ft3) 0.02832
~\ = m3and(in.Hg)25.4(^^.J = mmHg.

 ft3;                 \,in-H9/
Calculation Equations:
                                  Pstd
                                                Where:
                                      Tsfd = 298 K


                                      PsW = 760.0 mmHg
               2.
.VsW
• HBHBW^H

  e
                          FIGURE 7.  ORIFICE CALIBRATION  DATA SHEET.

-------
                      T013-88
                                '  | ' I I  I | I  I I I  | I I I I
   I  I I I  i i i  I I I i i i I .  i i ,  I i ,,,
0.0    0.25   0.50    0.75   1.00    1.25   1.50
 FIGURE 8.  ORIFICE METER CALIBRATION CURVE

-------
Performed by.

Date/Time	
Calibration Orifice.

Manometer S/N_
.S/N.
Ambient Temperature.

Bar. Press. _____
                                              .mrnHg
Sampler
S/N











Varlac
Setting V











Timer OK?
Yes/No










•———-————
Flow Rate Transfer Standard
Manometer
(n.H2O











Q a
std











Sampler Venturl Date
Magnehellc,
laH2O











Om,"











Comments











                                                                                                                00
                                                                                                                \o
 * From Calibration Curve For Flow Rate Transfer Standard (Section 11.2.1).

 b From Calibration Curve tor Venturl Tube Using Flow Rate Transfer Standard (Section 11.2A9).
                              FIGURE 9.   FIELD CALIBRATION DATA SHEET

-------
 Sampler Site
                                                         Before
                                                                                                       After
 Sampler Location.
 Date	•
                                     Barometric Pressure
                                     Ambient Temperature.
 Site.
Date.
Performed By.
Sampler
S/N












Sampling
Location
I.D.












Height
Above
Ground












Identification
No.
Rlter












XAD-2
or PUF












Sampling Period
Start












Stop












Totaling
Sampling
Time, min.












Pump Timer
Hr. Min.












Sampler Flow Check1
Manometer A H,
Inches of Water












QXS












M












Qms












Within
± 10%












                                                                                                               o
                                                                                                               I—>
                                                                                                               £
                                                                                                               o
1
  Must Be Performed Before and After Each Sampling Period
                                  Checked By.
                                  Date	
                                FIGURE 10.   FIELD TEST DATA  SHEET.

-------
                                       T013-91
                                              Adsorbent
                                            PUForXAD-2)
 Surrogate Standard
 Addition for GC/FID
 and GC/MS Analysis
   (Section 12.2.1)
                                      I
                        Soxhlet Extraction In Methylene Chloride
                              18 Hours/3 Cycles/Hr) or
                               Ether/Hexane Solvent
                                 (Section 12.2.1)
                         Drying with Anhydrous Sodium Sulfate
                                 (Section 12.2.2)
                           Kuderna-Danish (K-D) Evaporator
                          Attached with Macro Synder Column
                                 (Section 12.2.3)
Surrogate Standard
   Addition for
  HPLC Analysis
 (Section 12.2.1)
                                                                 Water Bath
                                                                  at60°C
                         Solvent Exchange to Cyclohexane by
                        K-D Apparatus with Macro Snyder Column
                                  (Section 12.3.2)
                                                                 Add 5 mL of
                                                                Cyclohexane
r
(No Extract Clean-up Required) Concentrate


toLOmL
4j —


1 (Extract Clean-Up
y Required)

f —
Pentane
Fraction
(Optional)



Silica Gel Column Topped with
Sodium Sulfate
(Section 12.4.1)
or Lobar Column
(Section (12.4.2)
f

If
Methylene Chloride/Pentane Fraction
Concentrated by K-D Apparatus to 1 mL
(Section 12.4.1 .3)
	 »J



—


Add 0.5 mL
Cyclohexane

Pentane
Elution
Methylene
Chloride/Pentane
Elution
Methanol
Elution

T
Methanol
Fraction
(Optional)

                                    Analysis by
                                    GC or HPLC
                                       J_
         Gas Chromatography
              Analysis
            (Section 13.0)
Flame lonization
 (Fl) Detection
 (Section 13.3)
                                                   Solvent Exchange to Acetonitrile
                                                         by K-D Apparatus
                                                           (Section 15.2)
                          Mass
                       Spectroscopy
                       (MS) Detection
                       (Section 14.0)

HPLC Analysis
(Section 15.4)

Ultra Violet
(UV) Detection





Fluorescence
(FL) Detection
       FIGURE  11.0.  SAMPLE  CLEAN-UP, CONCENTRATION,
                         SEPARATION AND ANALYSIS SEQUENCE.

-------
                               TO13-92
Injection
 Port
                   mm.
                      GC Column
                       (Capillary
                      or Packed)
                                     Flame
                                    lonization
                                      (Fl)
                                    Detector
                                      Mass
                                   Spectroscopy
                                      (MS)
                                       In
                                   SCAN Mode
       Flow
     Controller
                   Carrier
                   Gas
                   Bottle
    FIGURE  12.0
GC SEPARATION WITH SUBSEQUENT
FLAME IONIZATION (Fl) OR MASS
SPECTROSCOPY (MS) DETECTION.

-------
                    TO13-93

I
Select Internal Standards
Having Similar Behavior to ^
Compounds of Interest
(Section 13.4.2)
I
Prepare Calibration/
Internal Standards
(Section 13.4.2.1)
4
Inject Calibration Standards:
Calculate Response Factor (RF)
(Section 13.4.2.2)
4
Verify Working Calibration
Curve or RF Each Day —
(Section 13.4.2.6)

Establish Gas Chromatograph
Operating Parameters:
(Section 13.3)
Prepare Calibration Standards
(Section 13.4)
Tternal Standard ^ External Stand
Calibration Technique
• 	 (Section 13.4)

Calculate Retention
(Section 13.5)
i^
|
Introduce Extract Into
Gas Chromatograph by
Direct Injection
(Section 13.6.1)
\ r
Does Response Exceed
Linear Range
of System?
(Section 13.6.3.1)
^
Determine Identity and
Quantity of Each Analyte,
Using Appropriate Formulas
and Curves
(Section 13.6.3 and 17.2.1)
ard 	 1
Prepare Calibration Standards
^ for Each Analyte
of Interest
(Section 13.4.1)
^
Inject Calibration Standard:
Prepare Calibration Curve
or Calibration Factor (CF)
(Section 13.4.1.5)
1 '
Verify Working Calibration
Curve Each Day
(Section 13.4.1.7)



yes Dilute Extract
(Section 13.6.3.1)

FIGURE 13.0  GC CALIBRATION AND RETENTION
            TIME WINDOW DETERMINATION.

-------
                              TO13-94
t
            8
40
                        Retention Time, minutes

                Column:  3% OV-17 on Chromosorb W-AW-DCMS
                Program: 100 °C. 4 min., 8 ° per min. to 280 °C.
                Detector: Flame lonlzation
FIGURE 14.0  TYPICAL CHROMATOGRAM OF SELECTIVE PNAs
              BY GC EQUIPPED WITH Fl DETECTOR.

-------
                                              1013-95
                                 Establish Gas Chromatograph/
                            Mass Spectroscopy Operating Parameters:
                                 Prepare Calibration Standards
                                        (Section 14.2)
  Select Internal Standards
  Having Similar Behavior to
   Compounds of Interest
  Normally Deuterated PAHs
(Section 14.3.2 and 14.3.2.1)
                                    Tune GC/MS with DFTPP
                                         (Section 14.2)
Internal Standard
•4—
Calibration Technique
   (Section 14.3)
External Standard
           —*
                                                                   Prepare Calibration Standards
                                                                         for Each Analysis
                                                                           of Interest
                                                                         (Section 14.3.1)
     Prepare Calibration
         Standards
     (Section 14.3.2.4.1)
        Add Internal
         Standards
     (Section 14.3.1.10)
 Inject Calibration Standards:
Calculate Response Factor (RD)
      (Section 14.3.2.5)
  Verify Working Calibration
   Curve or RF Each Day
     (Section 14.3.2.6)
                                     Introduce Extract into
                                   GC/MS by Direct Injection
                                        (Section 14.4)
                                    Does Response Exceed
                                    Linear Range of System?
                                       (Section 14.4.3)
                                                                    Inject Calibration Standard:
                                                                     Prepare Calibration Curve
                                                                     or Calibration Factor (CF)
                                                                       (Section 14.3.1 .12)
                                                                    Verify Working Calibration
                                                                         Curve Each Day
                                                                       (Section 14.3.1 .13)
                                                              Yes
                                            Dilute Extract and
                                               Reanalyze
                                             (Section 14.4.3)
                                   Calculate Concentration of
                                      Each Analyte, Using
                                     Appropriate Formulas
                                   (Section 14.4.4 and 17.2.2)
Daily GC/MS Tuning
With DFTPP
(Section 14.5.1)
fe-

GC/MS Performance Test
(Section 14.5)
-^

12-Hr Calibration Verification
(Section 14.5.3)
                                         Daily 1-Point
                                     Calibration Verification
                                       (Section 14.5.2)
          FIGURE  15.0   GC/MS  CALIBRATION  AND ANALYSIS.

-------
                                            Guard    Analytical
                                            Column   Column
    Helium
nitrite Reservoir   Water Reservoir  High
with Fitter     \   with Filter       Pump
   Variable
  Wavelength
UV/Fluorescence
   Detector
                                                                                Data System
                                                                                and Recorder
o
I—"
V
                      Binary
                   Proportioning
                      Valve
         FIGURE 16.  IMPORTANT COMPONENTS OF AN  HPLC  SYSTEM.

-------
                              METHOD T014
    DETERMINATION  OF  VOLATILE  ORGANIC COMPOUNDS  (VOCs)  IN  AMBIENT  AIR
            USING  SUMMA® PASSIVATED CANISTER  SAMPLING AND  GAS
                         CHROMATOGRAPHIC  ANALYSIS

1.  Scope
    1.1  This document describes a procedure  for sampling  and  analysis
         of volatile  organic compounds  (VOCs) in ambient air.   The method
         is based on  collection of whole  air  samples in SUMMA® passivated
         stainless steel canisters.  The VOCs are subsequently separated
         by gas chromatography and measured by mass-selective  detector or
         multidetector techniques.  This method presents procedures for
         sampling into canisters to final pressures both above and below
         atmospheric pressure (respectively referred to as pressurized
         and subatmospheric pressure sampling).
    1.2  This method is  applicable to specific VOCs that have been tested
         and determined  to  be stable when stored in pressurized and sub-
         atmospheric pressure canisters.  Numerous compounds, many of
         which  are chlorinated  VOCs, have been  successfully tested for
         storage  stability  in pressurized canisters (1,2).  However,
         minimal  documentation  is  currently  available  demonstrating
         stability of  VOCs  in subatmospheric pressure  canisters.
     1.3  The organic  compounds  that  have been successfully collected in
          pressurized  canisters  by  this method are  listed  in Table 1.
         These compounds have been successfully measured  at the  parts  per
          billion by  volume  (ppbv)  level.
 2.  Applicable Documents
     2.1   ASTM Standards
          D1356 - Definition of Terms Related to Atmospheric  Sampling  and
                  Analysis                             „.',,.     u
          E260  - Recommended Practice for General  Gas Chromatography
                  Procedures                                      .
          E355  - Practice for Gas Chromatography Terms and  Relationships

     2.2  Other Documents
          U.S. Environmental Protection  Agency Technical Assistance Document (3)
          Laboratory and Ambient Air Studies  (4-17)

-------
                                                             Revision 1.0
                                                             June, 1988
                                METHOD T014
     DETERMINATION OF VOLATILE ORGANIC COMPOUNDS (VOCs)  IN AMBIENT AIR
  USING SUMMA® PASSIVATED CANISTER SAMPLING AND GAS CHROMATOGRAPHIC ANALYSIS

                                  OUTLINE

 1.  Scope
 2.  Applicable Documents
 3.  Summary of Method
 4.  Significance
 5.  Definitions
 6.  Interferences and Limitations
 7.  Apparatus
     7.1  Sample Collection
          7.1.1  Subatmospheric Pressure
          7.1.2  Pressurized
     7.2  Sample Analysis
          7.2.1  GC-MS-SCAN Analytical  System
          7.2.2  GC-MS-SIM Analytical  System
          7.2.3  GC-Multidetector Analytical  System
     7.3  Canister Cleaning System
     7.4  Calibration System and Manifold
 8.  Reagents and Materials
 9.  Sampling System
     9.1  System Description
          9.1.1  Subatmospheric Pressure Sampling
          9.1.2  Pressurized Sampling
          9.1.3  All Samplers
     9.2  Sampling Procedure
10.  Analytical System
     10.1 System Description
          10.1.1  GC-MS-SCAN System
          10.1.2  GC-MS-SIM System
          10.1.3  GC-Multidetector (GC-FID-ECD-PID) System
     10.2 GC-MS-SCAN-SIM System Performance Criteria
          10.2.1  GC-MS System Operation
          10.2.2  Daily GC-MS Tuning
          10.2.3  GC-MS Calibration
                  10.2.3.1  Initial  Calibration
                  10.2.3.2  Routine Calibration
     10.3 GC-FID-ECD System Performance Criteria (With Optional  PID)
          10.3.1  Humid Zero Air Certification
          10.3.2  GC Retention Time Windows Determination
          10.3.3  GC Calibration
                  10.3.3.1  Initial  Calibration
                  10.3.3.2  Routine Calibration
          10.3.4  GC-FID-ECD-PID System Performance Criteria
     10.4 Analytical Procedures
          10.4.1  Canister Receipt
          10.4.2  GC-MS-SCAN Analysis  (With Optional FID System)
          10.4.3  GC-MS-SIM Analysis (With Optional FID  System)
          10.4.4  GC-FID-ECD Analysis  (With Optional PID System)

-------
                              OUTLINE (Cont.)


11.  Cleaning and Certification Program
     11.1  Canister Cleaning and Certification
     11.2  Sampling System Cleaning and Certification
           11.2.1  Cleaning Sampling System Components
           11.2.2  Humid Zero Air Certification
           11.2.3  Sampler System Certification With Humid
                     Calibration Gas Standards
12.  Performance Criteria and Quality Assurance
     12.1  Standard Operating Procedures (SOPs)
     12.2  Method Relative Accuracy and Linearity
     12.3  Method Modification
           12.3.1  Sampling
           12.3.2  Analysis
     12.4  Method Safety
     12.5  Quality Assurance
           12.5.1  Sampling System
           12.5.2  GC-MS-SCAN-SIM System Performance Criteria
           12.5.3  GC-Multidetector System Performance Criteria

13.  Acknowledgements

14.  References

APPENDIX A - Availability of Audit Cylinders from U.S. Environmental
               Protection Agency (USEPA) to USEPA Program/Regional  Offices,
               State/Local  Agencies and Their Contractors
APPENDIX B - Operating Procedures for a Portable Gas Chromatograph  Equipped
               With a Photoionization Detector
APPENDIX C - Installation and Operating Procedures for Alternative  Air  Toxics
               Samplers

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                               T014-2
 Summary of Method

 3.1   Both  subatmospheric pressure and pressurized sampling modes use
      an initially  evacuated canister and a pump-ventilated sample line
      during sample  collection.  Pressurized sampling requires an addi-
      tional pump to provide positive pressure to the sample canister.
      A  sample  of ambient air is drawn through a sampling train comprised
      of components  that regulate the rate and duration of sampling into
      a  pre-evacuated SUMMA® passivated canister.
 3.2   After the air  sample is collected, the canister valve is closed,
      an  identification tag is attached to the canister, and the canis-
      ter is transported to a predetermined laboratory for analysis.
 3.3   Upon  receipt at the laboratory, the canister tag data is recorded
      and the canister is attached to the analytical  system.  During  analy-
      sis, water vapor is reduced in  the gas stream by a Nafion® dryer
      (if applicable), and the VOCs are then concentrated by collection
      in a cryogenically-cooled  trap.  The cryogen is then removed  and the
     temperature of the trap is raised.   The VOCs originally collected
      In the trap are revolatilized,  separated  on a GC column,  then de-
     tected by one  or more  detectors for identification and quantitation.
3.4  The analytical  strategy for Method  T014  involves using  a  high-
     resolution gas chromatograph  (GC)  coupled to  one or more  appro-
     priate GC detectors.   Historically,  detectors  for  a GC  have been
     divided into two groups:   non-specific  detectors and specific
     detectors. The non-specific detectors  include,  but  are not limited
     to, the  nitrogen-phosphorus detector  (NPD), the  flame  ionization
     detector  (FID), the  electron capture detector  (ECD)  and the photo-
     ionization detector  (PID).  The specific detectors  include the
     mass spectrometer  (MS)  operating in either  the  selected ion moni-
     toring (SIM) mode or the SCAN mode, or the  ion trap  detector.
     The use of these detectors  or a combination of these detectors
     as  part of an analytical scheme is determined by the required
     specificity and  sensitivity of the application.  While the non-
     specific  detectors are  less expensive per analysis and in some
     cases  more sensitive than the specific detector, they vary in
 -    specificity and  sensitivity for  a specific class of compounds.
     For  instance, if multiple halogenated compounds are targeted,

-------
                         T014-3

an ECD is usually chosen; if only compounds  containing  nitrogen
or phosphorus are of interest, a NPD can  be  used;  or,  if  a  variety
of hydrocarbon compounds are sought, the  broad  response of  the
FID or PID is appropriate.  In each of these cases,  however,  the
specific identification of the compound within  the class  is deter-
mined only by its retention time, which can  be  subject  to shifts
or to interference from other nontargeted compounds.  When  misiden-
tification occurs, the error is generally a  result of  a cluttered
chromatogram, making peak assignment difficult.  In  particular,
the more volatile organics (chloroethanes, ethyl toluenes, dichloro-
benzenes, and various freons) exhibit less well defined chromato-
graphic  peaks, leading to misidentification using non-specific
detectors.  Quantitative  comparisons indicate that the FID  is more
subject  to error than the ECD because the ECD is a much more  selec-
tive  detector for a  smaller class of compounds which exhibits a
stronger response.   Identification errors,  however, can be reduced
by:  (a)  employing simultaneous detection by different detectors
or  (b) correlating  retention times  from different GC columns  for
confirmation.  In either case,  interferences on the non-specific
detectors  can still  cause error  in  identifying a complex sample.
The  non-specific  detector system (GC-NPD-FID-ECD-PID), however,
has  been used for approximate quantitation  of  relatively clean
samples.  The nonspecific detector  system can  provide  a "snapshot"
of  the  constituents  in  the  sample,  allowing determination  of:
   -   Extent  of misidentification due  to  overlapping peaks,
   -   Position of the VOCs within or not  within the  concentration
      range of anticipated further analysis  by  specific detectors
      (GC-MS-SCAN-SIM)  (if not,  the  sample is further diluted), and
   -  Existence  of unexpected  peaks  which  need  further  identification
      by specific detectors.
 On the  other hand,  the use  of specific detectors  (MS  coupled to a
 GC)  allows positive compound identification, thus lending  itself
 to more specificity than the multidetector  GC.  Operating  in the
 SIM mode, the MS can readily approach the same sensitivity as the

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                          T014-4
 multidetector system, but its flexibility is limited.  For SIM
 operation, the MS is programmed to acquire data for a limited
 number of targeted compounds while disregarding other acquired
 information.  In the SCAN mode, however,  the MS becomes  a  universal
 detector, often detecting compounds which are not  detected  by
 the multidetector approach.   The GC-MS-SCAN  will  provide positive
 identification, while the GC-MS-SIM procedure provides quantitation
 of  a restricted "target  compound"  list  of VOCs.
 The analyst  often must decide whether to  use  specific or non-
 specific  detectors by considering  such  factors  as  project objectives,
 desired detection limits,  equipment  availability,  cost and
 personnel  capability  in  developing  an analytical strategy.
 A list of  some  of  the advantages and disadvantages associated
 with non-specific  and specific detectors may  assist the
 analyst in the  decision-making process.
           Non-Specific Multidetector Analytical System
        Advantages
o  Somewhat lower equipment
     cost than GC-MS
o  Less sample volume required
     for analysis
o  More sensitive
     -  ECD may be 1000 times
        more sensitive  than
        GC-MS
            Disadvantages
 o   Multiple detectors  to  calibrate
 o   Compound identification not
      positive
 o   Lengthy data interpretation
      (one hour each for analysis
     and data reduction)
 o   Interference(s) from co-eluting
     compound(s)
 o  Cannot identify unknown
     compounds
     -  outside range of cali-
        bration
     -  without standards
o  Does not differentiate
   targeted compounds from
   interfering compounds

-------
                         T014-5
               Specific Detector  Analytical  System
                          GC-MS-SIM
o
o
          Advantages
   positive compound  identification
   greater sensitivity than GC-MS-
     SCAN
o  less operator interpretation
     than for multidetector GC
o  can resolve co-eluting peaks
o  more specific than the multi-
     detector GC

                           GC-MS-SCAN
o  positive compound  identification
o  can identify all compounds
o  less operator interpretation
o  can resolve co-eluting  peaks
                                               Disadvantages
                                     o  can't identify non-specified
                                          compounds (ions)
                                     o  somewhat greater equipment
                                          cost than multidetector GC
                                     o  greater sample volume required
                                          than for multidetector GC
                                     o  universality of detector sac-
                                          rificed to achieve enhance-
                                          ment in sensitivity


                                     o  lower  sensitivity than GC-MS-
                                          SIM
                                     o  greater  sample  volume  required
                                          than for multidetector  GC
                                     o  somewhat greater equipment  cost
                                          than multidetector GC
The analytical finish for the measurement  chosen by the analyst
should provide a definitive identification and a precise quanti-
tation of volatile organics.  In a large part, the actual approach
to these two objectives is subject to equipment availability.
Figure 1 indicates some of the favorite options that are used as
an analytical finish.  The GC-MS-SCAN option uses a capillary
column GC coupled to a MS operated in a scanning mode and sup-
ported by spectral library search routines.  This option offers
the  nearest  approximation to unambiguous  identification and
covers a wide range  of compounds as defined by the completeness
of the spectral  library.  GC-MS-SIM mode  is limited to  a set of
target compounds which are user defined and is more sensitive
than GC-MS-SCAN  by virtue of  the longer dwell  times at  the
restricted  number of m/z  values.  Both these techniques, but
especially  the  GC-MS-SIM  option, can use  a supplemental  general
non-specific detector  to  verify/identify  the  presence  of VOCs.
Finally,  the option  labelled GC-multidetector  system  uses a

-------
                                   T014-6

          combination of retention time  and  multiple  general  detector  veri-
          fication  to identify compounds.  However, interference due to
          nearly identical  retention  times can  affect  system  quantitation
          when using  this  option.
          Due  to the  low concentrations  of VOCs encountered in urban air
          (typically  less  than  4 ppbv and the majority below  1 ppbv) along
          with their  complicated chromatograms, Method TO-14  strongly recommends
          the  specific detectors (GC-MS-SCAN-SIM) for positive identification
          and  for primary  quantitation to ensure that high-quality ambient
          data  is acquired.
          For  the experienced analyst whose analytical system is limited to the
          non-specific detectors, Section 10.3 does provide guidelines  and
          example chromatograms showing typical  retention times and calibra-
         tion  response factors, and utilizing the non-specific detectors
          (GC-FID-ECD-PID)  analytical  system as  the primary quantitative
         technique.
4.  Significance

    4.1  VOCs enter the  atmosphere from  a  variety  of  sources, including
         petroleum refineries, synthetic organic  chemical  plants,  natural
         gas processing  plants, and automobile  exhaust.  Many of these
         VOCs  are acutely  toxic; therefore,  their  determination in  ambient
         air is necessary  to  assess human  health  impacts.
    4.2  Conventional methods  for  VOC determination use  solid sorbent sampl-
         ing techniques.   The most widely  used solid  sorbent  is Tenax®.  An
         air sample is drawn through a Tenax®-filled  cartridge where certain
         VOCs  are trapped  on the polymer.  The sample cartridge is transferred
         to  a  laboratory and analyzed by GC-MS.
    4.3   VOCs  can also be  successfully collected in stainless steel canisters.
         Collection of ambient  air samples in canisters provides (1) conven-
         ient  integration  of ambient samples over a specific time period,
         (e.g.,  24 hours); (2)  remote sampling and central  analysis; (3)
         ease  of storing and shipping  samples; (4) unattended sample col-
         lection; (5)  analysis  of samples from multiple sites with  one
         analytical  system; and (6) collection of sufficient sample volume
        to  allow assessment of measurement precision  and/or analysis of

-------
                                 T014-7

        samples by several  analytical  systems.  However, care must be exer-
        cised in selecting, cleaning, and handling sample canisters and
        sampling apparatus to avoid losses or contamination of the samples,
        Contamination is a critical issue with canister-based sampling be-
       • cause the canister is the last element in the sampling train.
   4.4  Interior surfaces of the canisters are treated by the SUMMA®
        passivation process, in which a pure chrome-nickel oxide is
        formed on the surface.  This type of vessel has been used in the
        past  for sample collection and has demonstrated sample storage
        stability of many specific organic compounds.
   4.5  This  method can be applied to sampling and analysis of not only
        VOCs,  but also  some  selected semi volatile organic compounds
        (SVOCs).  The term "semivolatile  organic  compounds" is used to
        broadly  describe organic compounds that are too  volatile to be
        collected by  filtration  air  sampling  but  not volatile enough  for
        thermal  desorption from  solid  sorbents.   SVOCs  can generally  be
        classified  as those  with saturation vapor pressures  at 25°C  be-
        tween 10-1  and  10~7  mm Hg.   VOCs  are  generally  classified  as
        those organics  having saturated  vapor pressures  at 25°C  greater
        than  10"1 mm  Hg.
5.  Definitions
    Note:   Definitions  used  in  this document  and  in  any  user-prepared
    Standard Operating Procedures (SOPs)  should be consistent with ASTM
    Methods D1356, E260, and  E355.   All  abbreviations  and symbols within
    this method are  defined at  point of use.
    5.1   Absolute canister pressure = Pg+Pa,  where Pg = gauge pressure in
          the canister (kPa,  psi) and Pa = barometric pressure (see 5.2).
    5.2   Absolute pressure - Pressure measured with reference to absolute
          zero pressure (as opposed to atmospheric pressure), usually
          expressed  as kPa, mm Hg or psia.
    5.3   Cryogen -  A refrigerant used to obtain very low temperatures in
          the cryogenic trap of the analytical system.  A typical cryogen
          is  liquid  oxygen (bp -183.0°C) or liquid argon (bp -185.7°C).

-------
                              T014-8

5.4   Dynamic calibration - Calibration of an analytical system using
      calibration gas standard concentrations in a form identical  or
      very similar to the samples to be analyzed and by introducing
      such standards into the inlet of the sampling or analytical
      system in a manner very similar to the normal sampling or
      analytical process.
5.5   Gauge pressure - Pressure measured above ambient atmospheric
      pressure (as opposed to absolute pressure). Zero gauge pressure
      is equal to ambient atmospheric (barometric) pressure.
5.6   MS-SCAN - The GC is coupled to a MS programmed in the SCAN mode
      to scan all ions repeatedly during the GC run.  As used in the
      current context, this procedure serves as a qualitative identi-
      fication and characterization of the sample.
5.7   MS-SIM - The GC is coupled to a MS programmed to acquire data
      for only specified ions and to disregard all others.  This is
      performed using SIM coupled to retention time discriminators.
      The GC-SIM analysis provides quantitative results for selected
      constituents of the sample gas as programmed by the user.
5.8   Megabore* column - Chromatographic column having an internal  di-
      ameter (I.D.) greater than 0.50 mm.  The Megabore* column is a
      trademark of the J&W Scientific Co.  For purposes of this
      method, Megabore* refers to Chromatographic columns with 0.53
      mm I.D.
5.9   Pressurized sampling - Collection of an air sample in a canister
      with a (final)  canister pressure above atmospheric pressure,
      using a sample  pump.
5.10  Qualitative accuracy - The ability of an analytical  system to
      correctly identify compounds.
5.11  Quantitative accuracy - The ability of an analytical  system  to
      correctly measure the concentration of an identified compound.
5.12  Static calibration - Calibration of an analytical  system using
      standards in a  form different than the samples to be analyzed.
      An 'example of a static calibration would be injecting a small
      volume of a high concentration standard directly onto a GC
      column, bypassing the sample extraction and preconcentration
      portion of the  analytical  system.

-------
                                 T014-9
    5.13   Suba tiros pheric sampling - Collection of an air sample in an
          evacuated  canister at a (final) canister pressure below atmos-
          pheric pressure,  without the  assistance of a sampling pump.  The
          canister  is  filled as the internal canister pressure increases
          to  ambient or near ambient  pressure.  An auxiliary vacuum pump
          may be used as  part  of the  sampling system to  flush the inlet
          tubing prior to  or during sample  collection.
6.  Interferences  and Limitations
    6.1  Interferences can occur  in  sample  analysis  if moisture  accumu-
         lates in  the dryer (see  Section 10.1.1.2).  An  automated cleanup
         procedure that periodically heats  the  dryer to  about  100°C while
         purging with zero air eliminates any  moisture  buildup.  This pro-
         cedure does not degrade  sample integrity.
    6.2  Contamination may occur  in  the sampling system if canisters  are
         not properly cleaned before use.  Additionally, all  other sampling
         equipment  (e.g., pump and flow controllers) should be thoroughly
         cleaned to ensure that the filling apparatus will not contaminate
         samples.   Instructions for cleaning the canisters and certifying
         the field  sampling system are described in Sections 12.1 and 12.2,
          respectively.
    6.3   Because the  GC-MS analytical system employs a  Nafion* permeable
          membrane  dryer to remove water  vapor selectively from the sample
          stream, polar organic compounds may permeate concurrent with the
          moisture  molecule.   Consequently, the analyst  should quantitate
          his or her system with the  specific organic constituents under
          examination.
 7.  Apparatus
     7.1   Sample  Collection
          [Note:   Subatmospheric  pressure and pressurized  canister sampling
          systems  are commercially  available and have  been used  as part  of
          U.S. Environmental  Protection Agency's Toxics  Air Monitoring
          Stations  (TAMS), Urban  Air Toxic Pollutant Program (UATP),  and
          the non-methane organic compound  (NMOC) sampling and analysis
          program.]

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                           T014-10

7.1.1  Subatmospheric  Pressure  (See  Figure 2 Without Metal Bellows
       Type Pump)
       7.1.1.1   Sampling  inlet  line  - stainless steel tubing to
                connect the  sampler  to the sample inlet.
       7.1.1.2   Sample canister - leak-free stainless steel pressure
                vessels of desired volume (e.g., 6 L), with valve
                and SUMMA® passivated interior surfaces (Scientific
                Instrumentation Specialists, Inc., P.O. Box 8941,
                Moscow, ID 83843, or Anderson Samplers, Inc., 4215-C
                Wendell Dr., Atlanta, GA, 30336, or equivalent).
       7.1.1.3   Stainless steel  vacuum/pressure gauge - capable of '
                measuring vacuum (-100 to 0 kPa or 0 to 30 in Hg)
                and pressure (0-206 kPa or 0-30 psig) in the  sampling
                system (Matheson, P.O. Box 136, Morrow, GA 30200,
                Model  63-3704, or equivalent).   Gauges should be
               tested clean and leak tight.
       7.1.1.4   Electronic mass  flow controller -  capable  of  main-
               taining a constant flow rate  (_+ 10%)  over  a sampl-
                ing period of up to  24 hours  and under conditions
                of changing temperature  (20-40°C)  and humidity
                (Tylan Corp., 19220  S. Normandie Ave.,  Torrance,
               CA 90502,  Model  FC-260,  or equivalent).
      7.1.1.5  Particulate matter filter - 2-um sintered  stainless
               steel  in-line filter  (Nupro Co., 4800  E. 345th  St.,
               Willoughby,  OH 44094, Model SS-2F-K4-2,  or equiva-
               lent).
      7.1.1.6  Electronic timer - for unattended  sample collection
               (Paragon  Elect.  Co.,  606  Parkway Blvd.,  P.O.  Box 28,
               Twin Rivers,  WI  54201, Model 7008-00,  or equivalent).
      7.1.1.7  Solenoid  valve - electrically-operated,  bi-stable
               solenoid  valve (Skinner Magnelatch Valve,  New
               Britain,  CT,  Model V5RAM49710, or  equivalent) with
               Viton®  seat  and  o-rings.
      7.1.1.8  Chromatographic  grade stainless steel tubing and
               fittings - for interconnections  (Alltech Associates,
               2051 Waukegan Rd., Deerfield, IL 60015, Cat. #8125,

-------
                   T014-11
         or equivalent).   All such materials in contact with
         sample,  analyte,  and support  gases prior to analy-
         sis should be  chromatographic  grade stainless steel.
7.1.1.9  Thermostatically  controlled heater - to maintain
         temperature  inside  insulated  sampler enclosure above
         ambient  temperature (Watlow Co.,  Pfafftown, NC,
         Part 04010080, or equivalent).
7.1.1.10 Heater thermostat - automatically regulates heater
         temperature (Elmwood  Sensors, Inc., 500 Narragansett
         Park Dr., Pawtucket RI  02861, Model 3455-RC-0100-
         0222, or equivalent).
7.1.1.11 Fan - for cooling sampling system (EG&6 Rotron,
         Woodstock, NY, Model  SUZAI,  or equivalent).
7.1.1.12 Fan thermostat -  automatically regulates  fan  opera-
         tion (Elmwood Sensors,  Inc.,  Pawtucket, RI, Model
         3455-RC-0100-0244, or equivalent).
7.1.1.13 Maximum-minimum thermometer - records  highest and
         lowest temperatures during sampling  period  (Thomas
         Scientific, Brooklyn Thermometer Co.,  Inc.,
         P/N 9327H30, or equivalent).
7.1.1.14 Nupro stainless steel shut-off valve - leak  free,
         for vacuum/pressure gauge.
7.1.1.15 Auxiliary vacuum pump - continuously draws  ambient
         air to  be sampled through the inlet  manifold  at 10
         L/min.   or higher flow rate.  Sample is extracted
         from the manifold at a lower rate, and excess air
         is  exhausted.  [Note:  The use of higher inlet flow
         rates dilutes any contamination  present in  the inlet
         and  reduces the  possibility of sample contamination
         as  a result of contact with active adsorption sites
         on  inlet walls.]
7.1.1.16 Elapsed  time meter - measures duration of sampling
         (Conrac, Cramer  Div., Old Saybrook, CT, Type 6364,
         P/N 10082, or equivalent).
7.1.1.17 Optional fixed orifice, capillary, or adjustable
         micrometer!ng valve - may be used in lieu of the
         electronic flow  controller for grab samples or short
         duration time-integrated samples.  Usually appropri-
         ate only 1n situations where  screening ^mple  are
         taken  to assess  future sampling  activity.

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                                 T014-12
      7.1.2  Pressurized (Figure 2 With Metal  Bellows  Type  Pump and  Figure  3)
             7.1.2.1  Sample pump - stainless  steel, metal  bellows type
                      (Metal  Bellows Corp.,  1075  Providence  Highway,
                      Sharon, MA 02067,  Model  MB-151,  or  equivalent),
                      capable of 2 atmospheres  output  pressure.  Pump must
                      be free of leaks,  clean,  and uncontaminated by oil
                      or organic compounds.  [Note:  An alternative sampl-
                      ing system has  been developed by Dr. R. Rasmussen,
                      The Oregon Graduate Center  (18,19) and is  illustrated
                      in Figure  3.  This flow system uses, in order, a
                      pump, a mechanical flow regulator, and a mechanical
                      compensating flow restrictive device.  In this con-
                      figuration the pump is purged with a large sample
                      flow, thereby eliminating the need for an auxiliary
                      vacuum pump to flush the sample  inlet.  Interferences
                      using this configuration have been minimal.]
            7.1.2.2   Other supporting materials - all  other components  of
                     the pressurized sampling  system  (Figure 2  with  metal
                     bellows type pump and  Figure 3) are  similar to  compo-
                     nents  discussed in Sections  7.1.1.1  through 7.1.1.16.
7.2  Sample Analysis
     7.2.1   GC-MS-SCAN Analytical  System (See  Figure 4)
            7.2.1.1   The GC-MS-SCAN  analytical  system  must be capable of
                     acquiring  and processing  data in  the MS-SCAN mode.
            7.2.1.2   Gas chromatograph - capable  of sub-ambient  tempera-
                     ture programming  for the  oven, with other  generally
                     standard features such  as gas flow regulators, auto-
                     matic control  of valves and  integrator, etc.  Flame
                     ionization  detector optional.  (Hewlett Packard,
                     Rt. 41, Avondale, PA 19311, Model  5880A, with  oven
                     temperature  control and Level 4 BASIC programming,
                     or  equivalent.)
           7.2.1.3   Chromatographic dstector - mass-selective detector
                     (Hewlett Packard, 3000-T Hanover  St., 9B, Palo  Alto,
                     CA 94304, Model HP-5970 MS, or equivalent), equipped
                    with computer and appropriate software  (Hewlett
                    Packard, 3000-T Hanover St.,  9B,  Palo Alto, CA 94304,

-------
                    T014-13
         HP-216  Computer,  Quicksilver MS  software, Pascal
         3.0,  mass  storage 9133  HP Winchester with 3.5 inch
         floppy  disk,  or  equivalent).  The GC-MS is set  in
         the SCAN mode, where  the MS screens the sample  for
         identification and  quantitation  of VOC species.
7.2.1.4  Cryogenic  trap with temperature  control assembly -
         refer to Section 10.1.1.3 for complete description
         of trap and temperature control  assembly  (Nutech
         Corporation, 2142 Geer  St., Durham, NC, 27704,
         Model 320-01, or equivalent).
7.2.1.5  Electronic mass  flow  controllers (3) - maintain
         constant flow (for  carrier  gas  and  sample gas)  and
         to provide analog output  to monitor flow  anomalies
         (Tylan Model  260, 0-100 cm3/min, or equivalent).
7.2.1.6  Vacuum pump - general purpose  laboratory  pump,
         capable of drawing  the  desired  sample volume  through
         the cryogenic trap  (Thomas  Industries,  Inc.,  Sheboygan,
         WI, Model  107BA20,  or equivalent).
7.2.1.7  Chromatographic  grade stainless steel tubing  and
         stainless steel  plumbing  fittings -  refer to  Section
         7.1.1.8 for description.
7.2.1.8  Chromatographic  column  -  to provide  compound  separation
         such as shown in Table 5  (Hewlett Packard,  Rt.  41,
         Avondale, PA 19311, OV-1  capil lary column,  0.32 mm  x
         50 m with 0.88 urn crossi inked  methyl  silicone coating,
         or equivalent).
7.2.1.9  Stainless steel  vacuum/pressure gauge  (optional)  -
         capable of measuring vacuum (-101.3 to  0  kPa) and pres-
         sure (0-206 kPa) in the sampling system (Matheson,  P.O.
         Box  136, Morrow, GA 30200,  Model 63-3704, or  equiva-
         lent).  Gauges should be tested clean and leak tight.
7.2.1.10 Stainless steel  cylinder pressure regulators  - standard,
         two-stage cylinder regulators  with pressure gauges  for
         helium, zero air and hydrogen gas cylinders.
7.2.1.11 Gas  purifiers (3) - used to remove organic  impurities
         and  moisture from  gas streams (Hewlett  Packard, Rt. 41,
         Avondale, PA, 19311, P/N 19362  - 60500, or equivalent).

-------
                         T014-14
        7.2.1.12  Low dead-volume tee (optional)  -  used  to  split  the
                  exit flow from the GC  column  (Alltech  Associates,
                  2051 Waukegan Rd., Deerfield, IL  60015, Cat. #5839,
                  or equivalent).
        7.2.1.13  Nafion® dryer -  consisting  of Nafion tubing co-
                  axially mounted  within  larger tubing (Perma Pure
                  Products,  8  Executive  Drive, Toms River, NJ, 08753,
                  Model MD-125-48, or equivalent).  Refer to Section
                  10.1.1.2  for description.
        7.2.1.14  Six-port  gas  chromatographic valve - (Seismograph
                  Service Corp, Tulsa, OK, Seiscor Model  VIII, or
                  equivalent).
        7.2.1.15   Chart recorder  (optional) - compatible with the
                  detector output signals to record optional FID
                  detector response  to the sample.
        7.2.1.16   Electronic integrator (optional) - compatible
                  with the detector  output signal  of the  FID and
                  capable of integrating the area  of one  or  more
                  response peaks and  calculating peak  areas  cor-
                  rected for baseline drift.
7.2.2  GC-MS-SIM Analytical System (See  Figure  4)
       7.2.2.1   The GC-MS-SIM analytical  system  must  be capable  of
                 acquiring and processing data  in the  MS-SIM  mode.
       7.2.2.2   All components of the GC-MS-SIM  system  are  identi-
                 cal to Sections  7.2.1.2 through  7.2.1.16.
7.2.3  GC-Multidetector Analytical System (See Figure  5  and Figure 6)
       7.2.3.1   Gas chromatograph with  flame ionization and  elec-
                 tron capture  detectors  (photoionization detector
                 optional)  - capable of  sub-ambient temperature
                 programming for  the oven  and simultaneous opera-
                 tion of  all detectors,  and with  other generally
                 standard features such  as  gas flow regulators,
                 automatic  control of valves and  integrator, etc.
                 (Hewlett Packard, Rt. 41, Avondale, PA  19311,
                 Model  5880A,  with oven  temperature control  and
                 Level  4  BASIC  programming, or equivalent).

-------
                 T014-15
7.2.3.2  Chart recorders - compatible  with the  detector  output
         signals to record detector response to the  sample.
7.2.3.3  Electronic integrator - compatible with the detec-
         tor output signals and capable of integrating the
         area of one or more response peaks and calculating
         peak areas corrected for baseline drift.
7.2.3.4  Six-port gas chromatographic valve - (Seismograph Ser-
         vice Corp, Tulsa, OK, Seiscor Model VIII, or equivalent),
7.2.3.5  Cryogenic trap with temperature control assembly -
         refer  to  Section  10.1.1.3 for complete description of
         trap and  temperature  control assembly  (Nutech Corpora-
         tion,  2142 Geer  St.,  Durham, NC  27704, Model 320-01,
         or equivalent).
 7.2.3.6  Electronic mass  flow  controllers  (3)  - maintain  con-
         stant  flow  (for  carrier  gas,  nitrogen make-up  gas and
         sample gas)  and  to  provide  analog output to  monitor
         flow anomalies (Tylan Model  260, 0-100 cm3/min,  or
          equivalent).
 7.2.3.7   Vacuum pump - general purpose laboratory  pump,  capable
          of drawing the desired sample volume  through the cry-
          ogenic trap (see 7.2.1.6 for source and description).
 7.2.3.8  Chromatographic grade stainless steel tubing and stain-
          less  steel  plumbing fittings - refer to Section 7.1.1.8
          for description.
 7.2.3.9  Chromatographic column - to provide compound separation
          such  as  shown in Table 7.  (Hewlett Packard, Rt. 41,
          Avondale, PA  19311, OV-1 capillary column, 0.32
          mm  x  50  m with  0.88  urn crosslinked methyl silicone
          coating, or  equivalent).  [Note:  Other columns
           (e.g., DB-624)  can be used as long as the system
          meets user  needs.  The wider Megabore® column  (i.e.,
           0.53  mm  I.D.)  is less susceptible to plugging  as
           a result of  trapped  water, thus eliminating the
           need  for a  Nafion® dryer in  the analytical  system.
           The Megabore® column has sample capacity  approaching
           that  of  a  packed column, while  retaining  much of
           the peak resolution traits of narrower columns
           (i.e., 0.32 mm I.D.).

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                                T014-16

            7.2.3.10 Vacuum/pressure gauges (3) - refer to Section
                     7.2.1.9 for description.
            7.2.3.11 Cylinder pressure stainless steel  regulators -
                     standard, two-stage cylinder regulators with
                     pressure gauges for helium, zero air, nitrogen,
                     and hydrogen gas cylinders.
            7.2.3.12 Gas purifiers  (4) - used  to remove organic
                     impurities and moisture from gas streams (Hewlett-
                     Packard, Rt. 41, Avondale, PA,  19311, P/N 19362 -
                     60500, or equivalent).
            7.2.3.13 Low dead-volume tee -  used to split (50/50)  the
                     exit flow from the GC  column (Alltech Associates,
                     2051 Waukegan  Rd., Deerfield, IL 60015,  Cat.
                     #5839, or equivalent).
7.3  Canister Cleaning System (See  Figure 7)
     7.3.1  Vacuum pump - capable of evacuating sample  canister(s)  to
            an absolute pressure  of <0.05 mm Hg.
     7.3.2  Manifold - stainless  steel  manifold with  connections  for
            simultaneously cleaning several  canisters.
     7.3.3  Shut-off valve(s)  - seven (7) on-off toggle  valves.
     7.3.4  Stainless steel  vacuum  gauge -  capable of measuring vacuum
            in the manifold to  an absolute  pressure of 0.05 mm Hg or
            less.
     7.3.5  Cryogenic trap  (2  required)  - stainless steel  U-shaped  open
            tubular trap cooled with liquid oxygen or argon to prevent
            contamination from  back diffusion  of  oil  from  vacuum  pump
            and to provide  clean, zero  air  to  sample  canister(s).
     7.3.6  Stainless steel  pressure gauges (2)  -  0-345  kPa  (0-50 psig)
            to monitor zero  air pressure.
     7.3.7  Stainless steel  flow  control  valve  -  to regulate  flow of
            zero air into canister(s).
     7.3.8  Humidifier -  pressurizable water bubbler  containing high
            performance liquid  chromatography  (HPLC)  grade deionized
            water  or other  system capable of providing moisture to the
            zero air supply.
     7.3.9  Isothermal  oven  (optional)  for  heating canisters  (Fisher
            Scientific, Pittsburgh,  PA,  Model 349, or equivalent).

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                                T014-17
    7.4  Calibration System and Manifold (See Figure 8)

        7.4.1  Calibration manifold - glass manifold, (1.25 cm I.D. x 66 cm)

               with sampling ports and internal baffles for flow disturbance

               to  ensure  proper mixing.
        7.4.2  Humidifier - 500-mL impinger flask containing HPLC grade

               deionized  water.
        7.4.3  Electronic mass flow controllers - one 0 to 5 L/min and

               one 0  to 50 cm3/min  (Tylan  Corporation, 23301-TS Wilmington

               Ave.,  Carson, CA,  90745, Model  2160,  or equivalent).
        7.4.4  Teflon® filter(s)  - 47-mm Teflon®  filter  for particulate

               control,  best source.

8.  Reagents and  Materials

    8.1  Gas cylinders of  helium,  hydrogen, nitrogen, and  zero  air  -

         ultrahigh purity  grade,  best  source.
    8.2  Gas calibration standards -  cylinder(s)  containing  approximately

         10 ppmv  of each of the following  compounds  of interest:
         vinyl chloride
         vinylidene chloride
         l,l,2-trichloro-l,2,2-
           trifluoroethane
         chloroform
         1,2-dichloroethane
         benzene
         toluene
         Freon 12
         methyl chloride
         l,2-dichloro-l,l,2
         methyl bromide
         ethyl chloride
         Freon 11
         dichloromethane
         1,1-dichloroethane
         ci s-1,2-dichloroethylene
         1,2-dichloropropane
         1,1,2-trichloroethane
2-tetrafluoroethane
1,2-dibromoethane
tetrachloroethylene
chlorobenzene
benzyl chloride
hexachloro-1,3-butadiene
methyl chloroform
carbon tetrachloride
trichloroethylene
cis-l,3-dichloropropene
trans-1,3-di chloropropene
ethyl benzene
o-xylene
m-xylene
p-xylene
styrene
1,1,2,2-tetrachloroethane
1,3,5-trimethyl benzene
1,2,4-trimethylbenzene
m-dichlorobenzene
o-dichlorobenzene
p-dichlorobenzene
1,2,4-trichlorobenzene

-------
                                  T014-18

          The cylinder(s)  should  be traceable to a National Bureau of
          Standards  (NBS)  Standard Reference Material (SRM) or to a NBS/EPA
          approved Certified Reference Material (CRM).  The components may
          be  purchased in  one cylinder or may be separated into different
          cylinders.  Refer to manufacturer's specification for guidance on
          purchasing and mixing VOCs in gas cylinders.  Those compounds
          purchased should match one's own target list.
    8.3   Cryogen - liquid oxygen  (bp -183.0°C), or liquid argon (bp
          -185.7°C), best  source.
    8.4   Gas  purifiers - connected in-line between hydrogen, nitrogen, and
          zero air gas cylinders and system inlet line,  to remove moisture
          and  organic impurities from gas streams (Alltech Associates,
          2051 Waukegan Road, Deerfield,  Il_, 60015,  or equivalent).
    8.5   Deionized water - high performance liquid  chromatography  (HPLC)
          grade, ultrahigh purity (for humidifier),  best  source.
    8.6  4-bromofluorobenzene -  used for tuning 6C-MS,  best  source.
    8.7  Hexane - for cleaning sampling  system components, reagent  grade,
         best source.
    8.8  Methanol  -  for  cleaning  sampling  system components,  reagent grade,
         best source.
9.  Sampling System
    9.1  System Description
         9.1.1  Subatmospheric  Pressure  Sampling [See Figure  2 (Without Metal
                Bel lows  Type  Pump)]
                9.1.1.1   In  preparation  for  subatmospheric sample collec-
                        tion  in  a canister, the canister  is  evacuated to
                        0.05 mm  Hg.  When opened to the atmosphere con-
                        taining the VOCs  to be sampled, the  differential
                        pressure  causes the sample to flow into the can-
                        ister. This technique may be used to collect grab
                        samples  (duration of 10 to 30 seconds) or time-
                        integrated samples  (duration of 12 to 24 hours)
                        taken through a flow-restrictive  inlet (e.g.,
                        mass flow controller, critical  orifice).

-------
                        T014-19
       9.1.1.2  With a critical orifice flow restrictor, there will
                be a decrease in the flow rate as the pressure
                approaches atmospheric.  However, with a mass flow
                controller, the subatmospheric sampli-ng system can
                maintain a constant flow rate from full vacuum to
                within about 7 kPa (1.0 psi) or less below ambient
                pressure.
9.1.2  Pressurized Sampling [See Figure 2 (With Metal  Bellows Type Pump)]
       9.1.2.1  Pressurized sampling is used when longer-term inte-
                grated samples or higher volume samples are required.
                The sample is collected in a canister using a pump
                and flow control arrangement to achieve a typical
                103-206 kPa (15-30 psig) final  canister pressure.
                For example, a 6-liter evacuated canister can be
                filled at 10 cm3/min for 24 hours to achieve a final
                pressure of about 144 kPa (21 psig).
       9.1.2.2  In pressurized canister sampling, a metal bellows  type
                pump draws in ambient air from the sampling manifold
                to fill and pressurize the sample canister.
9.1.3  All  Samplers
       9.1.3.1  A flow control device is chosen to maintain a constant
                flow into the canister over the desired sample period.
                This flow rate is determined so the canister is filled
                (to about 88.1 kPa for subatmospheric pressure sampl-
                ing or to about one atmosphere above ambient pressure
                for pressurized sampling) over the desired sample
                period.  The flow rate can be calculated by
                                F =  P x V
                                     T x 60
                where:
                   F = flow rate (cm3/min).
                   P = final  canister pressure, atmospheres
                       absolute.  P is approximately equal  to
                                  + 1
qannp
1.
                          101.2

-------
                 T014-20

            V = volume of the canister (cm3).
            T = sample period (hours).
        For example,  if a 6-L canister is  to-be  filled
        to 202 kPa (2 atmospheres)  absolute  pressure  in
        24 hours, the flow rate can be calculated  by
              F = 2  x 6000  = 8.3 cm3/min
                  24  x 60
9.1.3.2  For automatic operation, the  timer  is wired  to  start
         and stop the pump at appropriate  times  for the  desired
         sample period.  The timer  must also  control  the sole-
         noid valve,  to open the valve when  starting  the pump
         and close the valve when stopping the pump.
9.1.3.3  The use of  the Skinner Magnelatch valve avoids  any
         substantial  temperature rise  that would occur with
         a conventional, normally closed solenoid  valve  that
         would have  to be energized during the entire sample
         period.  The temperature rise in  the valve could
         cause outgassing of organic compounds from the  Vi;
         valve seat material.  The  Skinner Magnelatch
         valve requires only a brief electrical pulse to
         open or close at the appropriate  start and stop
         times and therefore experiences no  temperature
         increase.  The pulses may  be  obtained either
         with an electronic timer that can be programmed
         for short (5 to 60 seconds) ON periods, or with
         a conventional  mechanical  timer and  a special
         pulse circuit.  A simple electrical  pulse circuit
         for operating the Skinner  Magnelatch solenoid valve
         with a conventional mechanical timer is illustrated
         in Figure 9(a).  However,  with this  simple circuit,
         the valve may operate unreliably  during brief
         power interruptions or if  the timer  is manually
         switched on  and off too fast.  A  better circuit in-
         corporating  a time-delay relay to provide more  re-
         liable valve operation is  shown in  Figure 9(b).

-------
                             TO14-21

            9.1.3.4   The connecting  lines between the  sample inlet and the
                     canister should  be  as  short as  possible to minimize
                     their volume.   The  flow  rate into the canister should
                     remain relatively constant over the entire sampling
                     period.   If  a  critical orifice  is used, some drop in
                     the flow rate  may occur  near the end of the sample
                     period as the  canister pressure approaches the final
                     calculated  pressure.
            9.1.3.5   As an option,  a  second electronic timer (see Sec-
                     tion 7.1.1.6)  may be used to start the auxiliary
                     pump several hours  prior to the sampling period
                     to flush and condition the inlet  line.
            9.1.3.6   Prior to field use, each sampling system must pass
                     a humid  zero air certification  (see Section 12.2.2).
                     All plumbing should be checked  carefully for leaks.
                     The canisters  must  also  pass a  humid zero air certi-
                     fication before use (see Section  12.1).
9.2  Sampling Procedure
     9.2.1  The sample canister  should be cleaned and  tested according
            to the procedure  in  Section  12.1.
     9.2.2  A sample collection  system is assembled  as shown in Figure 2
            (and Figure 3) and must meet certification requirements as
            outlined in Section  12.2.3.  [Note: The  sampling system
            should be contained  in  an appropriate enclosure.]
     9.2.3  Prior to locating the  sampling  system, the user may want to
            perform  "screening analyses" using a portable GC system,
            as outlined in Appendix B, to determine  potential volatile
            organics present  and  potential  "hot spots."  The information
            gathered from the portable GC screening  analysis would be
            used in  developing a  monitoring protocol,  which includes the
            sampling system location, based upon the "screening analysis"
            results.
     9.2.4  After "screening  analysis,"  the sampling system is located.
            Temperatures of ambient air  and sampler  box interior are
            recorded on canister  sampling field data sheet  (Figure 10).
            [Note:  The following  discussion  is related to Figure 2.]

-------
                        T014-22
9.2.5  To verify correct sample flow, a "practice" (evacuated)
       canister is used in the sampling system.  [Note:  For a
       subatmospheric sampler, the flow meter and practice can-
       ister are needed.  For the pump-driven system., the practice
       canister is not needed, as the flow can be measured at
       the outlet of the system.]  A certified mass flow meter
       is attached to the inlet line of the manifold, just in
       front of the filter.  The canister is opened.   The sampler
       is turned on and the reading of the certified  mass flow
       meter is compared to the sampler mass flow controller.
       The values should agree within +10%.  If not,  the sampler
       mass flow meter needs to be recalibrated or there is  a
       leak in the system.   This should be investigated and
       corrected.  [Note:   Mass flow meter readings may drift.
       Check the zero reading carefully and add or subtract  the
       zero reading when reading or adjusting the sampler flow
       rate, to compensate  for any zero drift.]  After two minutes,
       the desired canister flow rate is adjusted to  the proper
       value (as indicated  by the certified mass flow meter)  by
       the sampler flow control unit controller (e.g., 3.5
       cm3/min for 24 hr,  7.0 cm3/min for 12 hr).  Record final
       flow under "CANISTER FLOW RATE,"  Figure 10.
9.2.6  The sampler is turned off and the elapsed time meter  is
       reset to 000.0.  Note:   Any time  the sampler is turned
       off,  wait at least 30 seconds to  turn the sampler back on.
9.2.7  The "practice" canister and certified mass flow meter
       are disconnected and a clean certified (see  Section 12.1)
       canister is attached to the system.
9.2.8  The canister valve  and  vacuum/pressure gauge valve are opened.
9.2.9  Pressure/vacuum in the canister is recorded  on the canister
       sampling field data  sheet (Figure 10) as indicated by  the
       sampler vacuum/pressure gauge.
9.2.10 The vacuum/pressure  gauge valve is closed and  the maximum-
       minimum thermometer  is  reset to current temperature.   Time
       of day and  elapsed time meter readings are recorded on the
       canister sampling field data sheet.
9.2.11 The electronic timer is set to begin and stop  the sampling
       period at the appropriate times.   Sampling commences and
       stops by the programmed electronic timer.

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                                 T014-23

           9.2.12  After the  desired  sampling period, the maximum, minimum,
                   current  interior temperature and current ambient temper-
                   ature are  recorded on  the sampling field data sheet.  The
                   current  reading from the flow controller is recorded.
           9.2.13  At the end of  the  sampling period, the vacuum/pressure
                   gauge valve on the sampler is briefly opened and closed
                   and  the  pressure/vacuum is recorded  on the sampling field
                   data sheet. Pressure  should be close to desired pressure.
                   [Note:  For a  subatmospheric sampling system, if the
                   canister is at atmospheric pressure  when the field final
                   pressure check is  performed, the sampling period may be
                   suspect.  This information should be noted on the sampl-
                   ing  field  data sheet.] Time of day  and elapsed time
                   meter readings are also recorded.
           9.2.14  The  canister valve is  closed.  The sampling line is dis-
                   connected  from the canister and the  canister is removed
                   from the system.   For  a subatmospheric system, a certi-
                   fied mass  flow meter is once again connected to the in-
                   let  manifold in front  of the in-line filter and a "prac-
                   tice" canister is  attached to the Magnelatch valve of
                   the  sampling system.   The final flow rate is recorded
                   on the canister sampling field data  sheet (see Figure
                   10).  [Note: For a pressurized system, the final flow
                   may  be measured directly.]  The sampler is turned off.
           9.2.15  An identification  tag  is attached to the canister.  Can-
                   ister serial number, sample number,  location, and date
                   are  recorded on the tag.
10.  Analytical  System  (See Figures 4, 5  and 6)
     10.1  System Description
           10.1.1  GC-MS-SCAN System
                   10.1.1.1  The  analytical system is comprised of a GC
                             equipped with a mass-selective detector set
                             in the SCAN  mode (see Figure 4).  All ions
                             are  scanned  by the MS repeatedly during the

-------
     T014-24

 GC  run.  The  system includes a computer and
 appropriate software for data acquisition,
 data reduction, and data reporting.  A 400
 cm3  air sample is collected from the canister
 into  the analytical system.  The sample air is
 first passed  through a Nafion® dryer, through
 the  6-port chromatographic valve, then routed
 into a cryogenic trap.  [Note:  While the
 GC-multidetector analytical system does not
 employ a Nafion® dryer for drying the sample
 gas  stream, it is used here because the GC-MS
 system utilizes a larger sample volume and is
 far more sensitive to excessive moisture than
 the GC-multidetector analytical system.  Mois-
 ture can adversely affect detector precision.
 The Nafion® dryer also prevents freezing of
 moisture on the 0.32 mm I.D. column, which may
 cause column blockage and possible breakage.]
 The trap is heated (-160°C to 120°C in 60 sec)
 and the analyte is injected onto the OV-1 cap-
 illary column (0.32 mm x 50 m).  [Note:  Rapid
 heating of the trap provides efficient transfer
 of the sample components onto the gas chromato-
 graphic column.]  Upon sample injection onto
 the column, the MS computer is signaled by
the GC computer to begin detection of compounds
which elute from the column.  The gas stream
 from the GC is scanned within a preselected
 range of atomic mass units (amu).  For detec-
tion of compounds in Table 1, the range should
 be 18 to 250 amu, resulting in a 1.5 Hz repeti-
tion rate.   Six (6)  scans per eluting chromato-
graphic peak are provided at this rate.  The
 10-15 largest peaks  are chosen by an automated
data reduction program, the three scans nearest
the peak apex are averaged, and a background sub-
traction is performed.  A library search  is then
 performed and the top ten best matches for each
 peak are listed.  A qualitative characterization

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               1014-25

          of the  sample  is  provided  by this  procedure.  A
          typical  chromatogram  of  VOCs determined by 6C-MS-
          SCAN is illustrated in Figure  Ilia).
10.1.1.2  A Nafion® permeable membrane dryer is used to
          remove  water vapor selectively from the sample
          stream.  The permeable membrane consists  of
          Nafion® tubing (a copolymer of tetrafluoroethylene
          and fluorosulfonyl monomer) that is coaxially
          mounted within larger tubing.   The sample stream
          is passed through the interior of  the Nafion®
          tubing, allowing  water  (and other  light,  polar
          compounds) to  permeate through the walls  into a
          dry air purge  stream  flowing through the  annular
          space between  the Nafion® and  outer tubing.
          [Note:  To prevent excessive moisture build-up
          and any memory effects  in the  dryer, a  clean-
          up procedure involving periodic heating of  the
          dryer (100°C for 20 minutes) while purging  with
          dry zero air (500 cm3/min) should be implemented
          as part of the user's SOP manual.   The  clean-up
          procedure is repeated during each  analysis  (see
          Section 14, reference 7).  Recent  studies have
          indicated no substantial loss  of targeted
          VOCs utilizing the above clean-up procedure
          (7).  This cleanup procedure is particularly
          useful  when employing cryogenic preconcentration
          of VOCs with subsequent  GC analysis using a
          0.32 mm I.D. column  because excess accumulated
          water can cause trap  and column blockage  and
          also adversely affect detector precision.
          In addition, the improvement in water  removal
          from the sampling stream will  allow analyses
          of much larger volumes  of sample air  in the
          event that greater system sensitivity  is
          required for targeted compounds.]

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              T014-26

10.1.1.3  The packed metal  tubing  used  for  reduced  tem-
          perature trapping of VOCs  is  shown  in  Figure 12.
          The cooling unit  is  comprised of  a  0.32 cm  out-
          side diameter (O.D.)  nickel tubing  loop packed
          with 60-80 mesh Pyrex® beads  (Nutech Model
          320-01,  or equivalent).  The  nickel tubing  loop
          is wound onto a cyli ndrical ly formed tube heater
          (250 watt).  A cartridge heater (25 watt) is
          sandwiched between pieces  of  aluminum  plate
          at the trap inlet and outlet  to provide addi-
          tional heat to eliminate cold spots in the
                                                        »
          transfer tubing.   During operation, the trap
          is inside a two-section  stainless steel shell
          which is well  insulated.  Rapid heating
          (-150 to +100°C in 55 s) is accomplished  by
          direct thermal  contact between the  heater
          and the  trap tubing.   Cooling is  achieved by
          vaporization of the  cryogen.   In  the shell,
          efficient cooling (+120  to -150°C in 225  s)
          is facilitated by confining the vaporized
          cryogen  to the small  open  volume  surrounding
          the trap assembly.  The  trap  assembly  and
          chromatographic valve are  mounted on a
          baseplate fitted  into the  injection and
          auxiliary zones of the GC  on  an insulated
          pad directly above the column oven  when used
          with the Hewlett-Packard 5880 GC.   [Note:
          Alternative trap  assembly  and connection  to
          the GC may be  used depending  upon user's
          requirements.] The  carrier gas line is con-
          nected to the  injection  end of the  analytical
          column with a zero-dead-volume fitting that is
          usually  held in the  heated zone above  the GC
          oven. A 15 cm x  15  cm x 24 cm aluminum box
          is fitted over the sample  handling  elements
          to complete the package.  Vaporized cryogen
          is ve*ited*'4H£ough the top  of  the  box.

-------
                      T014-27
        10.1.1.4  As  an option,  the  analyst may  wish  to  split
                  the gas  stream exiting  the  column with  a
                  low dead-volume tee,  passing one-third
                  of  the sample  gas  (1.0  mL/min)  te the mass-
                  selective  detector and  the  remaining two-
                  thirds (2.0  mL/min) through a  flame
                  ionization detector,  as illustrated as  an
                  option in  Figure 4.   The use of the specific
                  detector (MS-SCAN) coupled  with the non-
                  specific detector  (FID) enables enhancement
                  of  data  acquired from a single analysis.   In
                  particular,  the FID provides the user:
                   o  Semi-real time picture of the  progress
                       of  the  analytical  scheme;
                   o  Confirmation  by  the concurrent MS
                       analysis  of other  labs that can provide
                       only  FID  results;  and
                   o  Ability to compare GC-FID with other
                       analytical laboratories with only  GC-
                       FID capability.
10.1.2  GC-MS-SIM System
        10.1.2.1  The analytical system is comprised  of  a GC
                  equipped with  an OV-1 capillary column  (0.32 mm
                  x 50 m)  and  a  mass-selective detector  set  in
                  the SIM  mode (see  Figure 4).   The GC-MS is
                  set up for automatic, repetitive analysis.
                  The system is  programmed to acquire data for
                  only the target compounds  and  to disregard
                  all  others.  The sensitivity is 0.1 ppbv for
                  a 250 cm-*  air  sample  with  analytical precision
                  of  about 5%  relative  standard  deviation.  Con-
                  centration of  compounds based  upon  a previously
                  installed  calibration table is reported by an
                  automated  data reduction program.   A Nafion®
                  dryer is also  employed  by this analytical sys-
                  tem prior  to cryogenic  preconcentration; there-
                  fore, many polar compounds  are not  identified
                  by  this  procedure.

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                      T014-28

        10.1.2.2  SIM analysis is based on a combination of reten-
                  tion times and relative abundances of selected
                  ions (see Table 2).  These qualifiers are stored
                  on the hard disk of the GC-MS computer and are
                  applied for identification of each chromato-
                  graphic peak.   The retention time qualifier is
                  determined to  be j^ 0.10 minute of the library
                  retention time of the compound.   The acceptance
                  level  for relative abundance is  determined to
                  be jf 15% of the expected abundance, except for
                  vinyl  chloride and methylene chloride, which
                  is determined  to be _+ 25%.  Three ions are mea-
                  sured  for most of the forty compounds.  When
                  compound identification is made  by the computer,
                  any peak that  fails any of the qualifying tests
                  is flagged (e.g., with an .*). All the data
                  should be manually examined by the analyst
                  to determine the reason for the  flag and
                  whether the compound should be reported as
                  found.  While  this adds some subjective
                  judgment to the analysis, computer-generated
                  identification problems can be clarified by
                  an experienced operator.  Manual  inspection
                  of the quantitative results should also be
                  performed to verify concentrations outside
                  the expected range.  A typical chromatogram
                  of VOCs determined by GC-MS-SIM  mode is
                  illustrated in Figure ll(b).
10.1.3  GC-Multidetector (GC-FID-ECD) System with  Optional PID
        10.1.3.1  The analytical  system (see Figure 5) is
                  comprised of a gas chromatograph equipped
                  with a capillary column and electron capture
                  and flame ionization detectors (see Figure 5).
                  In typical  operation, sample air from pressur-
                  ized canisters is vented past the inlet to
                  the analytical  system from the canister at a
                  flow rate of 75 cm3/min.  For analysis, only
                  35 cm3/min of  sample gas is used, while excess

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            T014-29
        is vented  to the atmosphere.   Sub-ambient
        pressure canisters  are connected  directly  to
        the inlet.  The sample gas stream is routed
        through a six port  chromatographic valve and
        into the cryogenic  trap for a total  sample
        volume of 490 cm3.   [Note: This represents a
        14 minute sampling  period at a rate of 35
        cm3/min.]  The trap (see Section 10.1.1.3)
        is cooled to -150°C by controlled release of
        a cryogen.  VOCs and  SVOCs are condensed on
        the  trap  surface while N2, 02, and  other sample
        components  are  passed to the  pump.  After the
        organic  compounds  are concentrated, the valve
        is  switched and the trap  is  heated.  The  revola-
        tilized compounds  are transported by  helium
        carrier gas at a rate of  4 cm3/min  to the
         head of the Megabore® OV-1 capillary  column
         (0.53 mm x 30 m).   Since the column initial
         temperature is at  -50°C, the VOCs and SVOCs
         are cryofocussed on the head of the column.
         Then, the oven temperature is programmed to
         increase and the VOCs/SVOCs in the carrier gas
         are chromatographically separated.  The carrier
          gas containing the separated VOCs/SVOCs is then
          directed to two parallel  detectors at a flow
          rate  of  2  cm3/min each.   The detectors sense
          the presence  of the  speciated VOCs/SVOCs, and
          the response  is recorded  by either a strip
          chart recorder or a  data  processing  unit.
10.1.3.2  Typical  chromatograms  of VOCs  determined by
          the 6C-FID-ECD analytical system are illus-
          trated in Figures ll(c)  and ll(d), respectively.
10.1.3.3  Helium is used as the carrier gas (4 cm3/min)
          to purge residual air from the trap at the
          end  of the sampling phase and to carry the
          revolatilized VOCs through the Megabore®
          GC column.  Moisture and organic  impurities
          are  removed  from the helium gas stream by a
           chemical  purifier installed in  the  GC (see

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               T014-30
           Section  7.2.1.11).  After exiting the OV-1  -
           Megabore® column, the carrier gas stream is
           split  to  the two detectors at rates of 2
           cm3/min  each.
 10.1.3.4   Gas  scrubbers containing Drierite® or silica
           gel  and  5A molecular sieve are used to remove
           moisture  and organic impurities from the zero
           air, hydrogen, and nitrogen gas streams.  [Note:
           Purity of gas purifiers is checked prior to use
           by passing humid zero-air through the gas purifier
           and  analyzing according to Section 12.2.2.] ,
 10.1.3.5   All  lines should be kept as short as practical. '
           All tubing used for the system should be chro-
          matographic grade stainless steel  connected
          with stainless steel  fittings.  After assembly,
          the system should be checked for leaks accord-
           ing to manufacturer's  specifications.
 10.1.3.6  The FID burner air, hydrogen,  nitrogen (make-
          up), and helium (carrier)  flow rates should
          be set according to the manufacturer's instruc-
          tions to obtain an optimal  FID response while
          maintaining a stable flame  throughout the  analy-
          sis.  Typical  flow rates are:  burner air,  450
          cm3/min;  hydrogen,  30  cm3/min;  nitrogen, 30
          cm3/min;  helium,  2  cm3/min.
10.1.3.7  The ECD nitrogen  make-up gas  and  helium carrier
          flow rates should be set according to manufac-
          turer's instructions to  obtain  an  optimal  ECD
          response.  Typical  flow rates  are:   nitrogen,
          76 cm3/min and  helium,  2 cm3/min.
10.1.3.8  The GC-FID-ECD  could be  modified to  include  a
          PID (see  Figure 6)  for  increased  sensitivity
          (20).  In the  photoionization  process,  a mole-
          cule is ionized by  ultraviolet  light  as  follows:
          R + hv  --> R  +  e-,  where R+ is the ionized species
          and a photon  is represented by hv, with  energy
          less than or  equal  to the ionization  potential  of

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    T014-31
the molecule.  Generally all  species  with an
ionization potential  less than the ionization
energy of the lamp are detected.  Because the
ionization potential  of all major components
of air (02, N2, CO, C02, and H20) is greater
than the ionization energy of lamps in general
use, they are not detected.  The sensor is
comprised of an argon-filled, ultraviolet (UV)
light  source where a portion  of the organic
vapors are  ionized in  the  gas stream.  A pair
of electrodes are contained  in  a  chamber adja-
cent  to  the  sensor.  When  a  positive  potential
is applied to the electrodes, any ions formed
by the absorption  of  UV  light are driven by
the created electronic field to the  cathode,
 and the  current  (proportional  to the organic
 vapor concentration)  is measured.  The PlD
 is generally used  for compounds having ioni-
 zation potentials less than the ratings  of
 the ultraviolet lamps.  This detector is
 used for determination of most chlorinated
 and oxygenated hydrocarbons, aromatic
 compounds, and high molecular weight aliphatic
 compounds.  Because the PID  is insensitive
 to methane, ethane, carbon monoxide, carbon
 dioxide, and water vapor, it is  an excellent
 detector.  The electron volt rating  is  applied
 specifically to the wavelength of the most
 intense  emission line of  the lamp's  output
 spectrum.   Some compounds with ionization
  potentials  above the  lamp rating can still
 be detected  due  to  the presence of  small
 quantities of more  intense  light.  A typical
  system configuration associated with the
  GC-FID-ECD-PID is  illustrated in Figure 6.
  This system is currently being used in  EPA's
  FY-88 Urban Air Toxics Monitoring Program.

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                            T014-32

10.2  GC-MS-SCAN-SIM System Performance  Criteria
      10.2.1   GC-MS  System Operation
              10.2.1.1   Prior  to  analysis, the GC-MS system is assembled
                        and  checked according to manufacturer's instruc-
                        tions.
              10.2.1.2   Table  3.0 outlines general operating conditions
                        for the GC-MS-SCAN-SIM system with optional FID.
              10.2.1.3   The GC-MS system is first challenged with humid
                        zero air  (see Section 11.2.2).
              10.2.1.4   The GC-MS and optional  FID system is acceptable
                        if it contains less than 0.2 ppbv of targeted
                        VOCs.
     10.2.2  Daily GC-MS Tuning (See Figure 13)
             10.2.2.1  At the beginning  of each day or prior to  a
                       calibration, the  GC-MS  system must be tuned to
                       verify that  acceptable  performance criteria are
                       achieved.
             10.2.2.2  For tuning the GC-MS, a  cylinder containing
                       4-bromofluorobenzene  is  introduced via  a
                       sample  loop  valve injection  system.   [Note:
                       Some systems  allow auto-tuning  to facilitate
                       this process.] The key  ions  and  ion  abundance
                       criteria that  must  be met are illustrated  in
                       Table 4.   Analysis  should not begin until
                       all  those  criteria  are met.
             10.2.2.3   The GC-MS  tuning  standard could also be used to
                       assess  GC  column  performance  (chromatographic
                       check)  and as  an  internal standard.  Obtain a
                       background correction mass spectra of 4-bromo-
                       fluorobenzene  and check that all key ions cri-
                       teria are met.  If the criteria are not achieved,
                       the analyst must  retune the mass spectrometer and
                       repeat the test until all criteria are achieved.
             10.2.2.4   The performance criteria must be achieved before
                       any samples, blanks or standards are analyzed.  If

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                     T014-33
                 any key ion abundance observed for the daily 4-
                 bromofluorobenzene mass tuning check differs by
                 more  than 10% absolute abundance from that observed
                 during the  previous  daily tuning, the instrument
                 must  be  retuned  or the sample and/or calibration
                 gases reanalyzed until the  above condition is met.
10.2.3  GC-MS Calibration  (See  Figure  13)
        [Note:  Initial and  routine calibration procedures  are
        illustrated in  Figure 13.]
        10.2.3.1  Initial  Calibration  - Initially, a multipoint  dy-
                  namic calibration (three  levels  plus  humid  zero
                  air)  is performed on the  GC-MS  system,  before
                  sample analysis, with the assistance  of a calibra-
                  tion system (see Figure 8).  The calibration sys-
                  tem  uses NBS traceable standards or NBS/EPA CRMs
                  in pressurized cylinders [containing a mixture
                  of the targeted VOCs at nominal  concentrations of
                  10 ppmv in nitrogen  (Section 8.2)] as working
                  standards to be diluted with humid zero air.  The
                  contents of the working standard cylinder(s) are
                  metered (2 cm3/min)  into the heated mixing chamber
                  where they are  mixed with  a 2-L/min humidified
                   zero air gas stream to achieve a nominal 10 ppbv
                   per  compound calibration mixture (see  Figure 8).
                   This nominal 10 ppbv standard mixture  is allowed
                   to flow and  equilibrate  for a minimum  of 30 min-
                   utes.   After the equilibration  period, the  gas
                   standard mixture is sampled and analyzed by the
                   real-time  GC-MS system  [see Figure 8(a)  and Sec-
                   tion 7.2.1].  The results  of the  analyses  are
                   averaged,  flow audits  are  performed  on the  mass
                   flow meters  and the calculated  concentration  com-
                   pared to  generated  values. After  the  GC-MS is
                   calibrated at  three concentration  levels,  a second
                   humid zero air sample is passed through the system
                   and analyzed.   The second  humid zero air test is
                   used to verify that the GC-MS  system is certified
                   clean (less than 0.2 ppbv of target compounds).

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                            T014-34
               10.2.3.2  As an alternative, a multipoint humid static
                        calibration (three levels plus zero humid air)
                        can be performed on the GC-MS system.  During
                        the humid static calibration analyses, three
                        (3) SUMMA® passivated canisters are filled
                        each at a different concentration between 1-20
                        ppbv from the calibration manifold using a
                        pump and mass flow control arrangement [see
                        Figure 8(c)].  The canisters are then delivered
                        to the GC-MS to serve as calibration standards.
                        The canisters are analyzed by the MS in the
                        SIM mode, each analyzed twice.  The expected
                        retention time and ion abundance (see Table
                        2 and Table 5) are used to verify proper opera-
                        tion of the GC-MS system.   A calibration re-
                        sponse factor is determined for each analyte,
                        as illustrated in Table 5, and the computer
                        calibration table is  updated with this infor-
                        mation, as illustrated in  Table 6.
              10.2.3.3  Routine Calibration -  The  GC-MS system is cal-
                        ibrated daily (and before  sample analysis)  with
                        a  one-point calibration.  The GC-MS system is
                        calibrated either with the dynamic calibration
                        procedure [see Figure  8(a)]  or with a  6-L SUMMA®
                        passivated canister filled with humid  calibration
                        standards from the calibration manifold (see
                        Section 10.2.3.2).  After  the single point  cali-
                        bration,  the  GC-MS analytical system is challenged
                        with  a humidified  zero gas stream to insure the
                        analytical  system returns  to specification  (less
                        than  0.2  ppbv  of selective organics).
ID.3  GC-FID-ECD System Performance Criteria  (With Optional  PID System)
      (See Figure 14)
      10.3.1   Humid Zero Air  Certification
              10.3.1.1  Before system  calibration  and sample analysis,
                        the GC-FID-ECD analytical  system is  assembled and
                        checked according  to manufacturer's  instructions.

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                        T014-35

       10.3.1.2  The 6C-FID-ECD system is first challenged with
                 humid zero air (see Section 12.2.2) and moni-
                 tored.
       10.3.1.3  Analytical systems contaminated with less than
                 0.2 ppbv  of  targeted VOCs  are  acceptable.
10.3.2 GC Retention Time Windows  Determination  (See Table 7)
        10.3.2.1   Before  analysis  can  be  performed, the  retention
                  time  windows must be established  for each
                  analyte.
        10.3.2.2  Make  sure the GC system is within optimum
                  operating conditions.
        10.3.2.3  Make three injections of the standard  contain-
                  ing all compounds for retention time window
                  determination.  [Note:  The retention time
                  window must  be  established for each analyte
                  every  72 hours  during continuous operation.]
         10.3.2.4  Calculate the standard  deviation of the three
                  absolute retention  times  for  each single com-
                  ponent standard.  The  retention window is
                  defined  as  the  mean plus  or minus three times
                  the  standard deviation  of the individual reten-
                   tion times  for  each standard.  In those  cases
                   where the standard  deviation  for a  particular
                   standard is zero, the laboratory must substi-
                   tute the standard deviation of a closely-
                   eluting, similar compound to develop  a valid
                   retention time window.
          10.3.2.5  The laboratory must calculate retention time
                   windows for each standard (see Table 7) on
                    each  GC column, whenever  a new GC column is
                    installed  or when  major  components of the GC
                    are changed.   The  data must  be  noted and re-
                    tained  in  a notebook  by  the  laboratory as
                    part  of the user SOP  and as  a quality assurance
                    check of the analytical  system.

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                         T014-36
10.3.3  GC Calibration
        [Note:   Initial  and  routine  calibration  procedures  are
        illustrated in  Figure 14.]
        10.3.3.1   Initial  Calibration  -  Initially, a multipoint
                  dynamic  calibration  (three  levels plus  humid
                  zero  air)  is  performed on the  6C-FID-ECD  sys-
                  tem,  before sample analysis, with the assist-
                  ance  of  a  calibration system (see Figure 8).
                  The calibration system uses NBS traceable
                  standards  or  NBS/EPA CRMs in pressurized
                  cylinders  [containing a mixture of the
                  targeted VOCs at nominal  concentrations of
                  10 ppmv  in  nitrogen (Section 8.2)] as working
                  standards  to  be diluted with humid zero air.
                  The contents  of the working standard cylinders
                  are metered (2 cm3/min) into the heated
                 mixing chamber where they are mixed  with a
                 2-L/min  humidified  zero air stream to achieve
                 a nominal 10 ppbv per compound calibration
                 mixture  (see Figure 8).   This nominal  10
                 ppbv standard mixture is  allowed to  flow and
                 equilibrate for an  appropriate amount of
                 time.   After the equilibration period, the gas
                 standard  mixture is sampled  and analyzed by
                 the GC-MS system [see Figure 8(a)].   The
                 results of  the analyses are  averaged,  flow
                 audits are  performed  on the  mass  flow control-
                 lers used to generate the  standards  and  the
                 appropriate response  factors  (concentration/
                 area counts) are calculated  for each  compound,
                 as illustrated in Table 5.   [Note:  GC-FIDs
                 are  linear  in  the 1-20 ppbv  range and  may
                 not  require repeated  multipoint calibra-
                 tions;  whereas, the GC-ECD will require
                 frequent  linearity evaluation.]  Table 5 out-
                 lines  typical  calibration response factors

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                           T014-37
                     and  retention times for 40 VOCs.  After the
                     GC-FID-ECD is calibrated at the three concen-
                     tration  levels, a  second humid zero air sample
                     is  passed through  the  system and-analyzed.  The
                     second humid  zero  air  test  is  used to verify
                     that the GC-FID-ECD  system  is  certified clean
                      (less than  0.2  ppbv  of target  compounds).
            10.3.3.2  Routine  Calibration  -  A one point  calibration
                      is performed daily on  the analytical  system to
                      verify the  initial multipoint  calibration  (see
                      Section 10.3.3.1).  The analyzers  (GC-FID-ECD)
                      are calibrated (before sample analysis)  using
                      the static calibration procedures (see Section
                      10.2.3.2) involving pressurized gas cylinders
                      containing low concentrations of the targeted
                      VOCs  (10 ppbv) in nitrogen.  After calibration,
                      humid zero  air is once  again  passed through the
                      analytical  system to  verify residual VOCs  are
                      not present.
     10.3.4  GC-FID-ECD-PID System Performance Criteria
             10.3.4.1  As an option,  the user may wish to  include a
                       photoionization  detector (PID)  to assist  in
                       peak identification and increase  sensitivity.
             10.3.4.2  This analytical  system is  presently being used
                       in U.S. Environmental Protection Agency's Urban
                       Air Toxic Pollutant Program (UATP).
             10.3.4.3  Preparation of the GC-FID-ECD-PID analytical
                       system is identical to the GC-FID-ECD system
                        (see Section 10.3).
             10.3.4.4  Table  8 outlines typical  retention times  (minutes)
                        for  selected organics  using  the GC-FID-ECD-PID
                        analytical  system.
10.4  Analytical  Procedures
      10.4.1  Canister Receipt
              10.4.1.1   The overall condition of  each  sample  canister
                        is observed.   Each canister should be  received
                        with an attached sample identification tag.

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                T014-38

  10.4.1.2  Each  canister is  recorded  in  the  dedicated
            laboratory  logbook.  Also  noted on the  identi-
            fication  tag  are  date received and initials
            of recipient.
  10.4.1.3   The pressure  of the canister is checked by
            attaching a pressure gauge to the canister
            inlet.  The canister valve is opened  briefly
           and the pressure (kPa,  psig)  is recorded.
           [Note: If pressure is  <83 kPa  (<12 psig),  the
           user  may wish  to pressurize the canisters,
           as an  option,  with zero  grade  nitrogen up  to
           137 kPa  (20  psig)  to ensure that enough
           sample is  available for  analysis.  However,
           pressurizing the canister can introduce  addi-
           tional error,  increase the minimum detection
           limit  (MDL), and is time consuming.  The user
           should weigh these limitations as part of his
           program objectives before pressurizing.]
          Final  cylinder pressure  is recorded on can-
          ister  sampling field data sheet  (see Figure 10)
10.4.1.4  If the  canister pressure  is  increased, a  di-
          lution  factor (DF)  is calculated and recorded
          on the  sampling data sheet.
              DF =   Ya_

          where:

              Xa = canister pressure  (kPa, psia) abso-
                   lute  before dilution.
              Ya = canister pressure (kPa, psia) abso-
                   lute after dilution.
         After sample analysis,  detected  VOC  concentra-
         tions are multiplied by the dilution factor
         to determine concentration in the sampled  air.

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                      TO14-39
10.4.2  GC-MS-SCAN Analysis  (With  Optional  FID  System)
       10.4.2.1  The analytical  system should be  properly  assem-
                 bled, humid zero  air certified (see  Section
                 12.3), operated (see Table 3), and calibrated
                 for accurate VOC  determination.
       10.4.2.2  The mass flow controllers are checked and adjusted
                 to provide correct flow rates for the system.
       10.4.2.3  The sample canister is connected to the inlet
                 of the GC-MS-SCAN (with optional FID) analytical
                 system.  For pressurized samples, a mass flow
                 controller is  placed on the canister and the
                 canister valve is opened and the  canister
                  flow is vented past  a tee  inlet to the analytical
                  system at  a  flow of  75 cm3/min  so that 40
                  cm3/min is  pulled through  the Nafion® dryer to
                  the  six-port  chromatographic  valve.  [Note:  Flow
                  rate is not  as important  as acquiring  sufficient
                  sample  volume.]   Sub-ambient  pressure  samples are
                  connected  directly  to the inlet.
        10.4.2.4  The GC oven and  cryogenic trap  (inject  position)
                  are cooled to their set  points  of -50°C  and
                  -160°C, respectively.
        10.4.2.5  As soon as the cryogenic trap reaches  its lower
                  set point of -160°C, the six-port chromatographic
                  valve is turned to its fill position to initiate
                  sample collection.
        10.4.2.6  A ten minute  collection period of canister sample
                  is  utilized.  [Note: 40 cm3/min x 10 min = 400
                  cm3  sampled canister contents.]
        10.4.2.7  After the sample is  preconcentrated in  the cry-
                  ogenic trap,  the GC  sampling valve  is cycled
                  to  the inject position  and the cryogenic trap
                   is  heated.  The trapped  analytes are thermally
                   desorbed  onto the  head  of the  OV-1  capillary
                   column (0.31  mm I.D.  x  50 m  length).  The GC
                   oven is  programmed to start  at -50°C  and after
                   2 min  to  heat to  150°C  at a  rate of 8°C per
                   minute.

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                       T014-40

         10.4.2.8  Upon sample injection onto the column, the MS
                   is signaled by the computer to scan the eluting
                   carrier gas from 18 to 250 amu,  resulting  in a
                   1.5 Hz repetition rate.   This  corresponds  to
                   about  6 scans  per eluting  chromatographic  peak.
         10.4.2.9  Primary identification  is  based  upon  retention
                   time and  relative abundance  of eluting  ions
                   as  compared to the  spectral  library stored on
                   the hard  disk of  the 6C-MS data  computer.
         10.4.2.10  The concentration  (ppbv) is  calculated  using
                   the previously established response factors
                   (see Section 10.2.3.2), as illustrated  in
                   Table 5.  [Note:  If the canister is diluted
                   before analysis, an appropriate multiplier is
                  applied to correct for the volume dilution of
                  the canister (Section 10.4.1.4).]
        10.4.2.11 The optional FID trace allows the analyst to
                  record  the progress of the analysis.
10.4.3  GC-MS-SIM Analysis (With  Optional  FID System)
        10.4.3.1   When the MS  is  placed  in the  SIM  mode  of
                  operation, the  MS  monitors  only preselected
                  ions, rather than  scanning  all masses  contin-
                  uously  between  two mass limits.
        10.4.3.2   As  a result,  increased sensitivity and improved
                  quantitative  analysis can be  achieved.
        10.4.3.3   Similar  to the GC-MS-SCAN configuration, the
                 GC-MS-SIM  analysis is based on a combination
                 of retention times and relative abundances of
                 selected ions (see Table 2 and Table 5).  These
                 qualifiers are stored on the hard  disk of
                 the GC-MS computer and are  applied for identi-
                 fication of each chromatographic peak.   Once
                 the GC-MS-SIM has  identified the peak,  a calibra-
                 tion response factor is used to  determine the
                 analyte's concentration.

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                    T014-41
       10.4.3.4  The individual analyses are handled in three
                phases:   data  acquisition, data reduction, and
                data  reporting.  The data acquisition software
                is  set  in the  SIM  mode, where  specific compound
                fragments are  monitored by the MS  at specific
                times in  the analytical run.   Data reduction
                 is  coordinated by  the  postprocessing macro pro-
                 gram  that is  automatically accessed after data
                 acquisition is completed  at  the  end of the GC
                 run.   Resulting ion profiles  are  extracted,  peaks
                 are identified and integrated, and an  internal
                 integration report is generated  by the program.
                 A reconstructed ion chromatogram for hardcopy
                 reference is prepared by  the program and various
                 parameters of interest such  as time, date,  and
                 integration constants are printed.  At the  com-
                 pletion  of the macro program, the data reporting
                 software  is accessed.  The appropriate calibra-
                 tion table (see Table 9)  is retrieved by the
                 data reporting program from the computer's  hard
                 disk storage  and  the proper retention time and
                 response factor parameters are applied to the
                 macro  program's integration file.  With refer-
                 ence to  certain pre-set acceptance criteria,
                 peaks  are automatically identified and quanti-
                 fied and a final  summary report  is prepared,
                 as illustrated  in Table 10.
10.4.4  GC-FID-ECD Analysis (With Optional PID  System)
        10.4.4.1 The  analytical  system should  be  properly assem-
                 bled,  humid  zero  air  certified  (see Section 12.2)
                  and  calibrated  through a dynamic standard cali-
                  bration  procedure (see Section  10.3.2).  The
                  FID  detector is lit and  allowed  to stabilize.
        10.4.4.2  Sixty-four minutes are required for each sample
                  analysis - 15 min for system initialization,  14
                  min  for sample collection,  30 min for analysis,
                  and  5 min for post-time, during which a report
                  is  printed.  [Note:  This may vary depending
                  upon  system configuration and programming.]

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                 T014-42
   10.4.4.3  The  helium and sample mass flow controllers are
            checked and adjusted to provide correct flow
            rates for the system.  Helium is used to purge
            residual air from the trap at the end of the
            sampling phase and to carry the revolatilized
            VOCs from the trap onto the GC column and into
            the FID-ECD.  The hydrogen, burner air,  and ni-
            trogen flow rates should also be  checked.   The
            cryogenic  trap  is connected and  verified to
            be operating  properly  while flowing  cryogen
            through  the  system.
  10.4.4.4   The  sample canister  is connected to  the inlet  of
            the  GC-FID-ECD analytical system.  The canister
            valve  is opened and  the canister flow is vented
            past  a tee inlet  to  the analytical system at 75
            cm3/min using a 0-500 cm3/min Tylan mass flow
            controller.  During analysis, 40 cm3/min of sample
            gas is pulled through the six-port chromatographic
            valve and routed  through the trap  at  the  appro-
           priate time while the extra  sample is vented.
           The VOCs  are  condensed  in the  trap  while  the
           excess flow is  exhausted  through an exhaust
           vent,  which assures  that  the sample air flow-
           ing through the trap  is at atmospheric pressure.
 10.4.4.5   The six-port valve is switched to the  inject
           position and the canister valve is closed.
 10.4.4.6  The electronic integrator is started.
 10.4.4.7  After the sample is preconcentrated on the trap,
          the trap is heated and the VOCs are thermally
          desorbed onto the  head of the capillary column.
          Since the column is at -50°C, the VOCs are cryo-
          focussed on the column.   Then, the  oven tempera-
          ture (programmed)   increases  and the VOCs  elute
          from the column  to the parallel  FID-ECD assembly.
10.4.4.8  The  peaks  eluting  from the detectors are iden-
          tified by  retention time  (see Table  7  and
          Table  8),  while  peak  areas are  recorded in area

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                                T014-43

                            counts.  Figures 15  and  16  illustrate  typical
                            response of the FID  and  ECD,  respectively,
                            for the forty (40)  targeted VOCs..   [Note:   Refer
                            to Table 7 for peak number  and identification.]
                  10.4.4.9  The response factors (see Section  10.3.3.1) are
                            multiplied by the area counts for  each peak
                            to calculate ppbv estimates for the unknown
                            sample.  If the canister is diluted before
                            analysis, an appropriate dilution  multiplier
                            (DF) is applied to correct  for the volume dilu-
                            tion of the canister (see Section  10.4.1.4).
                 10.4.4.10  Depending on the number of canisters to be
                            analyzed, each canister is analyzed twice
                            and the final concentrations for each analyte
                            are the averages of the two analyses.
                 10.4.4.11  However,  if the GC-FID-ECD analytical system
                            discovers  unexpected peaks which need further
                            identification  and  attention or overlapping
                            peaks  are  discovered, eliminating  possible quan-
                            titation,  the  sample should then be subjected
                            to  a GC-MS-SCAN  for positive  identification
                            and quantitation.
11.  Cleaning and Certification  Program
     11.1  Canister Cleaning and  Certification
           11.1.1  All canisters must  be clean  and free of  any  contaminants
                   before sample collection.
           11.1.2  All canisters  are leak  tested by  pressurizing them to
                   approximately 206 kPa (30 psig) with zero air.   [Note:
                   The canister cleaning system in Figure 7 can be used
                   for this task.]   The initial  pressure  is measured, the
                   canister valve  is closed, and the final  pressure is
                   checked after 24 hours.  If leak  tight, the pressure
                   should not  vary more than +_ 13.8  kPa (± 2 psig) over
                   the 24 hour period.
           11.1.3  A  canister cleaning system may be assembled as illus-
                   trated in Figure 7.  Cryogen is added to both the
                   vacuum pump and zero air supply traps.  The rani

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                        T014-44
          are connected  to  the manifold.  The vent shut-off valve
          and the  canister  valve(s) are opened to release any re-
          maining  pressure  in the canister(s).  The vacuum pump
          is  started and the vent shut-off valve is then closed
          and  the  vacuum shut-off valve is opened.  The canister(s)
          are  evacuated to < 0.05 mm Hg (for at least one hour).
          [Note:   On a daily basis or more often if necessary,  the
          cryogenic traps should be purged with zero  air to remove
          any trapped water from previous  canister cleaning cycles.]
 11.1.4   The vacuum and vacuum/pressure gauge  shut-off valves
         are closed and the zero air shut-off  valve  is opened
         to pressurize the  canister(s)  with  humid  zero air to
         approximately 206  kPa  (30  psig).   If  a  zero  gas  gener-
         ator system is used, the  flow  rate may  need  to  be
         limited to maintain the zero air quality.
 11.1.5  The zero shut-off  valve is  closed and the canister(s)
         is allowed to vent down to  atmospheric  pressure through
         the vent  shut-off  valve.  The vent shut-off  valve is
         closed.   Steps  11.1.3 through 11.1.5 are repeated two
         additional times for a  total of three (3) evacuation/
         pressurization cycles for each set of canisters.
 11.1.6   At the  end of the evacuation/pressurization cycle, the
         canister  is pressurized to 206 kPa (30 psig) with
         humid zero air.  The canister is  then analyzed by a
         GC-MS or  GC-FID-ECD analytical  system.  Any canister
         that  has  not tested clean (compared  to direct analysis
         of humidified zero air  of less  than  0.2 ppbv of targeted
         VOCs) should not be used.   As a "blank"  check of the
         canister(s) and cleanup procedure,  the final  humid zero
        air fill of 100% of the canisters  is  analyzed until the
        cleanup system and  canisters  are  proven  reliable  (less
        than 0.2 ppbv  of targets VOCs).  The check can then be
        reduced to a  lower  percentage of  canisters.
11.1.7  The canister is  reattached to the cleaning manifold and
        is then  reevacuated to  <0.05 mm Hg and remains in this
        condition until  used.  The canister valve is  closed.  The
        canister is removed from the cleaning system  and the can-
        ister connection  is capped with a stainless steel fitting.

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                           T014-45
             The canister is now ready for collection of  an  air  sample.
             An identification tag is attached to the neck of each
             canister for field notes, and chain-of-custody purposes.
     11.1.8  As an option to the humid zero air cleaning  procedures,
             the canisters could be heated in an isothermal  oven to
             100°C during Section 11.1.3 to ensure that lower mole-
             cular weight compounds (C2-Cs) are not retained on the
             walls of the canister.  [Note: For sampling  heavier, more
             complex VOC mixtures, the canisters should be heated to
             250°C during Section 11.1.3.7.]  Once heated, the canisters
             are evacuated to 0.05 mm Hg.  At the end of the heated/
             evacuated cycle, the canisters are  pressurized with humid
             zero  air and analyzed by the  GC-FID-ECD  system.  Any
             canister that has  not tested  clean  (less than 0.2 ppbv
             of targeted  compounds)  should not be used.  Once
             tested  clean, the  canisters  are  reevacuated to  0.05 mm
             Hg and  remain  in the evacuated state until used.
11.2  Sampling  System Cleaning and Certification
      11.2.1 Cleaning  Sampling  System Components
             11.2.1.1   Sample components are  disassembled  and  cleaned
                        before the sampler is  assembled.   Nonmetallic
                        parts are rinsed with  HPLC grade  deionized
                        water and dried in a vacuum oven  at 50°C.
                        Typically, stainless steel  parts  and fittings
                        are cleaned by placing them in a  beaker of
                        methanol in an ultrasonic bath for 15 minutes.
                        This procedure is repeated with hexane as
                        the solvent.
              11.2.1.2  The parts are then rinsed with HPLC grade
                        deionized water and dried in a vacuum oven
                        at 100°C  for 12 to 24 hours.
              11.2.1.3  Once the  sampler is assembled, the entire
                        system  is purged with humid zero air for 24
                        hours.
       11.2.2  Humid  Zero Air  Certification
              [Note:  In the  following sections,  "certification" is
              defined as  evaluating the  sampling system with humid

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puts AHoiasa                                            . .    ,
K    '                                            jeded pepAoaj
                     T014-46
       zero air and  humid calibration gases  that  pass  through
       all  active components of the sampling system.   The  sys-
       tem is "certified" if no significant  additions  or dele-
       tions (less than 0.2 ppbv of targeted compounds) have
       occurred when challenged with the test gas stream.]
       11.2.2.1  The cleanliness of the sampling  system is deter-
                 mined  by testing the sampler with humid zero air
                 without an evacuated gas cylinder, as follows.
       11.2.2.2  The calibration system and  manifold are assem-
                 bled,  as illustrated in Figure 8. The sampler
                 (without an evacuated gas cylinder)  is con-
                 nected to the manifold and  the zero air
                 cylinder activated to generate a humid gas
                 stream (2 L/min) to the calibration manifold
                 [see Figure 8(b)].
       11.2.2.3  The humid zero gas stream passes through  the
                 calibration manifold, through the sampling
                 system (without an evacuated canister) to a
                 6C-FID-ECD analytical  system at  75 cm3/min
                 so  that 40 crrrVmin is pulled through  the  six-
                 port valve and routed through the cryogenic
                 trap (see Section 10.2.2.1) at the appropriate
                 time while the extra sample is vented.  [Note:
                 The exit of the sampling system  (without  the
                 canister) replaces the canister  in Figure 4.]
                 After  the sample (400 ml) is preconcentrated
                 on  the.trap, the trap is heated  and the VOCs
                 are thermally desorbed onto the  head  of the
                 capillary column.  Since the column  is at
                 -50°C, the VOCs are cryofocussed on the col-
                 umn.  Then, the oven temperature (programmed)
                 increases and the VOCs begin to  elute and are
                 detected by a GC-MS (see Section 10.2) or the
                 GC-FID-ECD (see Section 10.3).  The analytical
                 system should not detect greater than 0.2 ppbv
                 of  targeted VOCs in order for the sampling
                 system to pass the humid zero air certification

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                     T014-47
                 test.  Chromatograms of a certified sampler
                 and contaminated sampler are illustrated in
                 Figures 17(a) and (b), respectively.  If
                 the sampler  passes the humid zero air test,
                 it  is  then tested with humid calibration gas
                 standards containing selected VOCs at concen-
                 tration  levels  expected in field sampling (e.g.,
                 0.5 to 2  ppbv)  as outlined in Section 11.2.3.
11.2.3  Sampler System  Certification with Humid Calibration Gas
        Standards
        11.2.3.1  Assemble  the dynamic calibration system and
                 manifold as  illustrated in Figure  8.
        11.2.3.2  Verify that  the calibration  system is clean
                  (less than  0.2  ppbv  of targeted compounds)
                  by sampling  a humidified  gas stream, without
                  gas calibration standards, with a  previously
                  certified clean canister  (see Section 12.1).
        11.2.3.3  The assembled dynamic  calibration  system  is
                  certified clean if  less  than 0.2  ppbv of
                  targeted compounds  are found.
        11.2.3.4  For generating the  humidified calibration
                  standards, the calibration gas cylinder(s)
                  (see  Section 8.2) containing nomin*!  concen-
                  trations of 10 ppmv in nitrogen of S'lected
                  VOCs, are attached  to the calibration system, as
                  outlined in Section 10.2.3.1.  The gas  cylinders
                  are opened and the gas mixtures are passed
                  through 0 to 10 cm3/min certified mass  flow
                  controllers to generate ppb levels of
                  calibration standards.
        11.2.3.5  After the appropriate equilibrium period, attach
                  the  sampling system (containing a certified
                  evacuated canister) to the manifold, as illus-
                  trated  in Figure 8(a).

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                                 T014-48

                    11.2.3.6  Sample? the dynamic calibration gas stream with
                             the sampling system according to Section 9.2.1.
                             [Note: To conserve generated calibration gas,
                             bypass the canister sampling system manifold
                             and attach the sampling system to the calibra-
                             tion gas stream at the inlet of the in-line
                             filter of the sampling system so the flow
                             will be less than 500 cm3/min.]
                   11.2.3.7  Concurrent with the sampling system operation,
                             realtime monitoring of the calibration gas
                             stream is accomplished by the on-line GC-MS
                             or GC-multidetector analytical  system
                             [Figure 8(b)] to provide reference concentra-
                             tions  of generated VOCs.
                   11.2.3.8  At the end of the sampling period (normally same
                             time period used for anticipated  sampling),
                             the sampling system canister is analyzed and
                             compared  to the reference GC-MS or GC-multi-
                             detector  analytical system to determine  if
                             the concentration of  the targeted VOCs was
                             increased or decreased by the sampling
                             system.
                   11.2.3.9  A  recovery of between  90% and 110%  is  expected
                             for all targeted  VOCs.
12.  Performance Criteria and Quality  Assurance
     12.1  Standard Operating Procedures  (SOPs)
           12.1.1   SOPs  should  be generated  in  each laboratory describing
                   and documenting the  following activities:   (1) assembly,
                   calibration,  leak check,  and  operation  of specific
                   sampling systems and  equipment used;  (2)  preparation,
                   storage, shipment,  and  handling  of  samples;  (3)  assembly,
                   leak-check, calibration,  and  operation  of the analytical
                   system,  addressing the  specific  equipment used;  (4)  can-
                   ister  storage and cleaning;  and  (5)  all aspects  of data
                   recording  and processing, including  lists of computer
                   hardware and  software used.

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                           T014-49
      12.1.2   Specific  stepwise  instructions  should be provided in
              the SOPs  and should  be  readily  available to and under-
              stood by  the laboratory personnel  conducting the work.
12.2  Method  Relative Accuracy and Linearity
      12.2.1   Accuracy  can be determined  by injecting VOC standards
              (see Section 8.2)  from an  audit cylinder into  a sampler.
              The contents are then analyzed  for the  components con-
              tained in the audit canister.  Percent  relative accuracy
              is calculated:
                      % Relative Accuracy =  V - x  x 100
                                               X
                     Where:  Y = Concentration of the targeted
                                 compound recovered from sampler.
                             X = Concentration of VOC targeted
                                 compound in the NBS-SRM or
                                 EPA-CRM audit cylinders.
       12.2.2   If the relative accuracy does  not fall between 90 and
               and 110  percent, the field sampler should be  removed
               from use,  cleaned,  and  recertified according  to initial
               certification  procedures outlined in Section  11.2.2
               and Section 11.2.3.  Historically, concentrations of
               carbon tetrachloride,  tetrachloroethylene, and hexachlo-
               robutadiene have  sometimes been  detected  at lower  con-
               centrations when  using parallel  ECD  and FID detectors.
               When these three compounds  are present  at concentrations
               close to calibration levels, both detectors usually
               agree on the reported  concentrations.   At concentrations
               below 4 ppbv,  there is a  problem with  nonlinearity of
               the ECD.  Plots of concentration versus peak  area  for
               calibration compounds detected by the  ECD have shown
               that the curves are nonlinear  for carbon  tetrachloride,
               tetrachloroethylene, and hexachlorobutadiene, as  illus-
               trated in Figures 18(a) through 18(c).  Other targeted
               ECD and FID compounds scaled  linearly for the range 0 to
               8 ppbv, as  shown for chloroform in Figure 18(d).   For
               compounds that are not linear over the calibration

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                               T014-50

               range,  area  counts  generally  roll  off between 3 and 4
               ppbv.   To  correct for the nonlinearity of these compounds,
               an  additional  calibration step  is  performed.  An evacuated
               stainless  steel  canister is pressurized with calibration
               gas  at  a nominal concentration  of 8 ppbv.  The sample
               is then diluted  to  approximately 3.5 ppbv with zero air
               and  analyzed.  The  instrument response factor (ppbv/area)
               of the ECD for each of the three compounds is calculated
               for  the 3.5 ppbv sample.  Then, both the 3.5 ppbv and
              the  8 ppbv response factors  are entered into the ECD
              calibration table.   The software for the Hewlett-Packard
              5880 level  4 GC is  designed  to accommodate multilevel
              calibration entries, so the  correct response factors
              are automatically calculated for concentrations  in  this
              range.
12.3  Method Modification
      12.3.1  Sampling

              12.3.1.1  The sampling system  for pressurized canister
                       sampling could be modified to use a lighter,
                       more compact pump.   The pump currently being
                       used  weighs about  16 kilograms (35 Ibs).  Com-
                       mercially  available  pumps that could be used
                       as  alternatives to the prescribed sampler pump
                       are  described below.   Metal Bellows MB-41 pump:
                       These pumps are cleaned at the factory; however,
                       some  precaution should be taken with the circu-
                       lar  (4.8 cm diameter) Teflon® and stainless steel
                       part directly under the flange.  It is often
                       dirty when  received and should be cleaned
                       before use.  This part is  cleaned by removing
                       it from the pump, manually cleaning with
                       deionized  water,  and  placing  in a vacuum oven
                       at 100°C for at least 12 hours.   Exposed
                       parts of the pump  head  are also  cleaned with
                       swabs and  allowed to  air dry.   These pumps  have

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                      T014-51
                 proven to be very reliable; however, they are
                 only useful up to an outlet pressure of about
                 137 kPa  (20 psig).  Neuberger Pump:  Viton gas-
                 kets or  seals must be specified -with this pump.
                 The "factory direct" pump  is received contaminated
                 and leaky.  The pump is cleaned by disassembling
                 the pump head (which consists of three stainless
                 steel  parts and two gaskets), cleaning the gaskets
                 with deionized water and drying in a vacuum oven,
                 and remachining (or manually lapping) the sealing
                 surfaces of the stainless  steel parts.  The stain-
                 less steel parts  are then  cleaned with methanol,
                 hexane,  deionized water and heated in a vacuum
                 oven.  The cause  for most  of the problems with
                 this pump has been scratches on the metal parts
                 of the pump head.  Once this rework procedure is
                 performed, the pump is considered clean and can
                 be used  up to about 240 kPa (35 psig) output pres-
                 sure.  This pump  is utilized in the sampling sys-
                 tem illustrated in Figure  3.
        12.3.1.2 Urban  Air Toxics  Sampler
                 The  sampling system described  in this method can
                 be modified like  the sampler in EPA's FY-88 Urban
                 Air Toxics Pollutant Program.  This particular
                 sampler  is described in Appendix C  (see Figure  19).
12.3.2  Analysis
        12.3.2.1  Inlet  tubing from the  calibration manifold could
                  be heated to 50°C (same temperature as the cali-
                 bration  manifold) to prevent condensation on the
                 internal walls of the  system.
        12.3.2.2 The  analytical strategy for Method  TO-14 involves
                  positive identification and quantitation by
                 GC-MS-SCAN-SIM mode of operation with optional
                  FID.   This  is a highly specific and sensitive
                 detection technique.   Because  a specific detec-
                  tor  system (GC-MS-SCAN-SIM)  is more complicated
                  and  expensive than  the use of  non-specific detectors

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       T014-52

  (GC-FID-ECD-PID),  the analyst may  want  to  perform
  a screening analysis  and preliminary  quantisation
  of VOC species in  the sample, including  any  polar
  compounds,  by utilizing the  GC-multidetector
  (GC-FID-ECD-PID)  analytical  system prior to  GC-MS
  analysis.   This  system can be used for  approximate
  quantitation. The GC-FID-ECD-PID  provides a "snap-
  shot"  of the constituents in  the sample, allow-
  ing  the  analyst  to determine:
    -  Extent  of misidentification due  to  over-
      lapping peaks,
    -  Whether the constituents  are  within the
      calibration range  of the  anticipated
      GC-MS-SCAN-SIM analysis  or does  the
      sample  require further dilution, and
    -  Are there unexpected peaks which need further
      identification through GC-MS-SCAN or are
      there peaks of interest  needing attention?
 If  unusual peaks are observed from the GC-FID-ECD-
 PID system, the analyst then performs a GC-MS-SCAN
 analysis.  The  GC-MS-SCAN will provide positive
 identification  of suspect peaks from the GC-FID-
 ECD-PID system.  If no unusual peaks are identi-
 fied and  only a select number of VOCs are of con-
 cern, the analyst can then proceed to GC-MS-SIM.
 The GC-MS-SIM is used for final quantitation of
 selected VOCs.  Polar compounds, however, cannot
 be identified by the GC-MS-SIM due to the use
 of a Nafion® dryer to remove  water from the  sample
 prior to analysis.  The dryer  removes polar  com-
 pounds along with the water.   The analyst often
 has to make this decision incorporating project
 objectives,  detection limits,  equipment availa-
 bility,  cost and personnel capability in  develop-
 ing an analytical  strategy.   Figure  20  outlines
the use  of the GC-FID-ECD-PID  as a "screening"
 approach,  with the GC-MS-SCAN-SIM for final
 identification and quantitation.

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                            T014-53

12.4  Method Safety
      This procedure may involve  hazardous  materials,  operations,  and
      equipment.   This method does not  purport  to  address  all  of the
      safety problems associated  with its  use.   It is  the  user's respon-
      sibility to establish appropriate safety  and health  practices
      and determine the applicability of regulatory limitations  prior
      to the implementation of this  procedure.   This should  be part
      of the user's SOP manual.
12.5  Quality Assurance (See Figure  21)
      12.5.1  Sampling System
              12.5.1.1  Section 9.2  suggests that  a portable GC system be
                        used as a "screening analysis" prior to locating
                        fixed-site samplers (pressurized  or  subatmospheric),
              12.5.1.2  Section 9.2  requires pre and post-sampling meas-
                        urements with a certified  mass flow  controller
                        for flow verification of sampling system.
              12.5.1.3  Section 11.1 requires all  canisters  to be  pres-
                        sure tested  to 207 kPa  _+ 14 kPa (30  psig ± 2 psig)
                        over a period of 24 hours.
              12.5.1.4  Section 11.1  requires  that all canisters  be
                        certified clean (containing less  than 0.2  ppbv
                        of targeted  VOCs)  through  a humid zero air certi-
                        fication program.
              12.5.1.5  Section 11.2.2 requires all field sampling systems
                        to be certified initially  clean (containing  less
                        than 0.2 ppbv of targeted  VOCs) through a  humid
                        zero air certification  program.
              12.5.1.6  Section 11.2.3 requires all field sampling sys-
                        tems to pass an initial humidified calibration
                        gas certification [at VOC  concentration levels
                        expected in  the field (e.g., 0.5  to  2 ppbv)]
                        with a percent recovery of greater than 90.
      12.5.2  GC-MS-SCAN-SIM System Performance Criteria
              12.5.2.1  Section 10.2.1 requires the GC-MS analytical
                        system to be certified  clean (less than 0.2

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                      T014-54
                  ppbv of targeted VOCs)  prior to sample analy-
                  sis, through a humid zero air certification.
        12.5.2.2  Section 10.2.2 requires the daily tuning  of
                  the GC-MS with 4-bromofluorobenzene (4-BFB)
                  and that it meet the key ions and ion  abun-
                  dance critera (10%)  outlined in Table  5.
        12.5.2.3  Section 10.2.3 requires both an initial multi-
                  point humid static  calibration (three  levels
                  plus humid zero air) and a daily calibration
                  (one point) of the  GC-MS analytical  system.
12.5.3  GC-Multidetector System Performance Criteria
        12.5.3.1  Section 10.3.1 requires the GC-FID-ECD analyti-
                  cal system, prior to analysis, to be certified
                  clean (less than 0.2 ppbv of targeted  VOCs)
                  through a humid zero air certification.
        12.5.3.2  Section 10.3.2 requires that the GC-FID-ECD
                  analytical  system establish retention  time
                  windows for each analyte prior to sample  analy-
                  sis,  when a new GC  column is installed, or
                  major components of  the GC system altered
                  since the previous  determination.
        12.5.3.3  Section 8.2 requires that all  calibration
                  gases be traceable  to a National  Bureau of
                  Standards (NBS)  Standard Reference Material
                  (SRM)  or to a NBS/EPA approved Certified
                  Reference Material  (CRM).
        12.5.3.4  Section 10.3.2 requires that the retention
                  time  window be established throughout  the
                  course of a 72-hr analytical  period.
        12.5.3.5  Section 10.3.3 requires both an  initial multi-
                  point  calibration (three levels  plus humid
                  zero  air)  and a  daily calibration (one point)
                  of  the GC-FID-ECD analytical  system  with zero
                  gas dilution of  NBS  traceable  or NBS/EPA CRMs
                  gases.  [Note:   Gas  cylinders  of VOCs  at the
                  ppm and ppb level are available  for  audits
                  from  the USEPA,  Environmental  Monitoring Systems

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                                T014-55

                             Laboratory,  Quality Assurance Division, MD-77B,
                             Research  Triangle  Park,  NC  27711,  (919)541-4531.
                             Appendix  A outlines five groups of  audit gas
                             cylinders available from USEPA.]
13.  Acknowledgements
     The determination of volatile and some semi-volatile  organic  compounds
     in ambient air is a complex task, primarily because of the wide  variety
     of compounds of interest and  the  lack of standardized sampling and
     analytical procedures.  While there are numerous procedures for  sampling
     and analyzing VOCs/SVOCs in ambient air, this method draws upon  the
     best aspects of each one and combines them into a standardized method-
     ology.  To that end, the following individuals contributed to the
     research, documentation and peer review of this manuscript.

-------
Topic

Sampling System
Analytical System

     GC-FID-ECD
Contact

Mr. Frank McElroy
Mr. Vinee Thompson
                      Dr. Bill McClenny
                      Mr. Joachim Pleil
                      Mr. Tom Merrifield
                      Mr. Joseph P. Krasnec
Dr. Bill McClenny
Mr. Joachim Pleil
                      Ms. Karen D. Oliver
     GC-FID-ECD-PID  Dave-Paul Dayton
                     JoAnn Rice
            Address

U.S. Environmental Protection Agency
Environmental  Monitoring Systems Laboratory
MD-77
Research Triangle Park, N.C. 27711

U.S. Environmental Protection Agency
Environmental  Monitoring Systems Laboratory
MD-44
Research Triangle Park, N.C. 27711

Anderson Samplers, Inc.
4215-C Wendell Drive
Atlanta, GA 30336

Scientific Instrumentation Specialists, Inc.
P.O. Box 8941
Moscow, Idaho, 83843
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
MD-44
Research Triangle Park, N.C. 27711

Northrop Services, Inc.
Environmental Sciences
P.O. Box 12313
Research Triangle Park, N.C. 27709

Radian Corporation
P.O. Box 13000
Progress Center
Research Triangle Park, N.C. 27709
Telephone No.

919-541-2622
919-541-3791
                                                                     919-541-3158
                                                                     919-541-4680
                                                                     1-800-241-6898-
                                                                     208-882-3860-
919-541-3158
919-541-4680
                                                                     919-549-0611
                                                                     919-481-0212
                                                                                         CTV

-------
   Topic

       GC-MS-SCAN-SIM
Canister Cleaning
Certification and
VOC Canister Storage
Stability
       Cryogenic
       Sampling
       Unit
       U.S. EPA
       Audit Gas
       Standards
 Contact

Dr. Bill McClenny
Mr. Joachim Pleil
                        Mr. John V. Hawkins
Mr. Vince Thompson
                        Dr. Bill  McClenny
                        Mr. Joachim Pleil
                        Dave-Paul Dayton
                        JoAnn Rice
                        Dr. R.K.M. Jayanty
Mr. Lou Ballard
Mr. Pete Watson
                        Mr. Joachim Pleil
Mr. Bob Lampe
            Address

U.S. Environmental Protection Agency
Environmental  Monitoring Systems Laboratory
MD-44
Research Triangle Park, N.C. 27711

Research Triangle Laboratories, Inc.
P.O. Box 12507
Research Triangle Park, N.C. 27709

U.S. Environmental Protection Agency
Environmental  Monitoring Systems Laboratory
MD-77
Research Triangle Park, N.C. 27711

U.S. Environmental Protection Agency
Environmental  Monitoring Systems Laboratory
MD-44
Research Triangle Park, N.C. 27711

Radian Corporation
P.O. Box 13000
Progress Center
Research Triangle Park, N.C. 27709

Research Triangle Institute
P.O. Box 12194
Research Triangle Park, N.C. 27709

NuTech Corporation
2806 Cheek Road
Durham, N.C., 27704

U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
MD-44
Research Triangle Park, N.C. 27711

U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
MD-77B
Research Triangle Park, N.C.27711
Telephone No.

919-541-3158
919-541-4680
                                                                      919-544-5775
919-541-3791
                                                                      919-541-3158
                                                                      919-541-4680
                                                                      919-481-0212
                                                                      919-541-6000
                                                                                              919-682-0402
                                                                      919-541-4680
                                                                                              919-541-4531
                                                                                                                     i
                                                                                                                     en

-------
                                 T014-58
14.  REFERENCES
 1.  K. D. Oliver, J. D. Pleil, and W. A.  McClenny,  "Sample  Integrity  of
     Trace Level Volatile Organic Compounds in  Ambient  Air Stored  in
     SUMMA® Polished Canisters," Atmospheric Environ.   20:1403,  1986.

 2.  M. W. Holdren and D. L. Smith, "Stability  of Volatile Organic  Compounds
     While Stored in SUMMA® Polished Stainless  Steel  Canisters," Final
     Report, EPA Contract No. 68-02-4127,  Research Triangle  Park,  NC,
     Battel le Columbus Laboratories, January, 1986.

 3.  Ralph M. Riggin, Technical Assistance Document  for Sampling and
     Analysis of Toxic Organic Compounds in Ambient  Air, EPA-600/4-83-027,
     U.S. Environmental Protection Agency, Research  Triangle Park,  NC,  1983.

 4.  Ralph M. Riggin, Compendium of Methods for the  Determination  of Toxic  '
     Organic Compounds in Ambient Air. EPA-600/4-84-041, U.S. Environmental
     Protection Agency, Research Triangle  Park, NC,  1986.

 5.  W. T. Winberry and N. V. Til ley,  Supplement to  EPA-600/4-84-041;
     Compendium of Methods for the Determination of  Toxic Organic  Compounds
     in Ambient Air. EPA-600/4-87-006, U.S. Environmental Protection Agency,
     Research Triangle Park, NC, 1986.

 6.  W. A. McClenny, J. D  Pleil, J. W. Holdren, and  R. N. Smith,  "Automated
     Cryogenic Preconcentration and Gas Chromatographic Determination  of
     Volatile Organic Compounds," Anal. Chem.   56:2947, 1984.

 7.  J. D. Pleil and K. D. Oliver, "Evaluation  of  Various Configurations of
     Nafion Dryers:  Water Removal  from Air Samples  Prior to Gas Chromatographic
     Analysis," EPA Contract No.  68-02-4035, Research  Triangle Park,  NC,
     Northrop Services, Inc.- Environmental  Sciences, 1985.

 8.  K. D. Oliver and J. D.  Pleil,  "Automated Cryogenic Sampling  and  Gas
     Chromatographic Analysis of Ambient Vapor-Phase  Organic Compounds:
     Procedures and Comparison Tests," EPA Contract  No. 68-02-4035, Research
     Triangle Park, NC, Northrop Services, Inc.- Environmental Sciences, 1985.

 9.  W. A. McClenny and J. D. Pleil, "Automated Calibration  and Analysis of
     VOCs with a Capillary Column Gas  Chromatograph  Equipped for Reduced Temper-
     ature Trapping," Proceedings of the 1984. Air  Pollution  Control
     Association Annual Meeting, San Francisco, CA,  June 24-29, 1984.

10.  W. A. McClenny, J. D. Pleil, T. A. Lumpkin, and  K. D. Oliver,  "Update
     on Canister-Based Samplers for VOCs," Proceedings  of the 1987  EPA/APCA
     Symposium on Measurement of Toxic and Related Air  Pollutants,  May, 1987
     -APCA Publication VIP-8, EPA 600/9-87-010.

11.  J. D. Pleil, "Automated Cryogenic Sampling and  Gas Chromatographic
     Analysis of Ambient Vapor-Phase Organic Compounds: System Design,"
     EPA Contract No. 68-02-2566, Research Triangle  Park, NC, Northrop
     "Services, Inc.- Environmental  Sciences, 1982.

-------
                                 T014-59


12.  K. D. Oliver and J.  D.   Pleil,  "Analysis of Canister Samples Collected
     During the CARB Study in August 1986," EPA Contract No. 68-02-4035,
     Research Triangle Park,  NC,  Northrop  Services,  Inc.- Environmental
     Sciences, 1987.

13.  J. D. Pleil  and K. D. Oliver,  "Measurement of Concentration Variability
     of Volatile Organic  Compounds  in Indoor Air: Automated Operation of a
     Sequential Syringe Sampler and  Subsequent GC/MS  Analysis," EPA Contract
     No. 68-02-4444, Research Triangle Park, NC, Northrop Services, Inc. -
     Environmental  Sciences,  1987.

14.  J. F. Walling, "The  Utility of Distributed Air  Volume Sets When
     Sampling Ambient Air Using Solid Adsorbents," Atmospheric Environ.,
     18:855-859, 1984.

15.  J. F. Walling, J. E. Bumgarner, J. D. Driscoll,  C. M. Morris, A. E. Riley,
     and L. H. Wright, "Apparent Reaction  Products Desorbed From Tenax Used
     to Sample Ambient Air,"  Atmospheric Environ., 20:  51-57, 1986.

16.  Portable Instruments User's Manual for Monitoring  VOC Sources, EPA-
     340/1-88-015, U.S. Environmental  Protection Agency, Office of Air
     Quality Planning and Standards, Washington, DC,  June, 1986.

17.  F. F. McElroy, V. L. Thompson, H. G.  Richter, A Cryogenic Preconcentra-
     tion - Direct FID (PDFID) Method for  Measurement of NMOC in the Ambient
     Air. EPA-600/4-85-063, U.S. Environmental Protection Agency, Research
     Triangle Park, NC, August 1985.

18.  R. A. Rasmussen and  J. E. Lovelock,  "Atmospheric Measurements Using
     Canister Technology," J. Geophys. Res., 83: 8369-8378, 1983.

19.  R. A. Rasmussen and  M.A.K. Khalil, "Atmospheric Halocarbons:  Measure-
     ments and Analysis of Selected Trace  Gases," Proc. NATO ASI on Atmos-
     pheric Ozone, BO: 209-231.

20.  Dave-Paul Dayton and JoAnn Rice, "Development and  Evaluation of a
     Prototype Analytical System for Measuring Air Toxics," Final Report,
     Radian Corporation for the U.S. Environmental Protection Agency,
     Environmental Monitoring Systems Laboratory, Research Triangle Park,
     NC 27711, EPA Contract No. 68-02-3889, WA No. 120, November, 1987.

-------
TABLE 1.  VOLATILE ORGANIC COMPOUND DATA SHEET
COMPOUND (SYNONYM)
Freon 12 (Dichlorodifluoromethane)
Methyl chloride (Chloromethane)
Freon 114 (l,2-Dichloro-l,l,2,2-
tetrafluoroethane)
Vinyl chloride (Chloroethylene)
Methyl bromide (Bromomethane)
Ethyl chloride (Chloroethane)
Freon 11 (Trichlorof luoromethane)
Vinylidene chloride (1,1-Dichloroethene)
Dichloromethane (Methylene chloride)
Freon 113 (l,l,2-Trichloro-l,2,2-
trifluoroethane)
1,1-Dichloroethane (Ethylidene chloride)
cis-l,2-Dichloroethylene
Chloroform (Trichloromethane)
1,2-Dichloroethane (Ethylene dichloride)
Methyl chloroform (1,1,1-Trichloroethane)
Benzene (Cyclohexatriene)
Carbon tetrachloride (fetrachloromethane)
1,2-Dichloropropane (Propylene
dichloride)
Trichloroethylene (Trichloroethene)
cis-l,3-Dichloropropene (cis-1,3-
dichloropropylene)
FORMULA
C12CF2
CH3C1
C1CF2CC1F2
CH2=CHC1
CHsBr
CH3CH2C1
CClsF
C2H2C12
CH2C12
CF2C1CC12F
CH3CHC12
CHC1=CHC1
CHC13
C1CH2CH2C1
CHsCCla
C6H6
CC14
CH3CHC1CH2C1
C1CH=CC12
CH3CC1=CHC1

MOLECULAR
WEIGHT
120.91
50.49
170.93
62.50
94.94
64.52
137.38
96.95
84.94
187.38
98.96
96.94
119.38
98.96
133.41
78.12
153.82
112.99
131.29
110.97

BOILING
POINT (°C)
-29.8
-24.2
4.1
-13.4
3.6
12.3
23.7
31.7
39.8
47.7
57.3
60.3
61.7
83.5
74.1
80.1
76.5
96.4
87
76

MELTING
POINT (°C)
-158.0
-97.1
-94.0
-1538.0
-93.6
-136.4
-111.0
-122.5
-95.1
-36.4
-97.0
-80.5
-63.5
-35.3
-30.4
5.5
-23.0
-100.4
-73.0


CAS
NUMBER
74-87-3
75-01-4
74-83-9
75-00-3
75-35-4
75-09-2
74-34-3
67-66-3
107-06-2
71-55-6
71-43-2
56-23-5
78-87-5
79-01-6


                                                                                 I
                                                                                 o>
                                                                                 o

-------
TABLE 1.  VOLATILE ORGANIC COMPOUND DATA SHEET  (cont.)
____ 	 r
COMPOUND (SYNONYM)
trans-l,3-Dichloropropene (cis-1,3-
Dichloropropylene)
1,1,2-Trichloroethane (Vinyl trichloride)
Toluene (Methyl benzene)
1 ,2-Dibremoethane (Ethyl ene di bromide)
Tetrachloroethylene (Perchloroethylene)
Chlorobenzene (Phenyl chloride)
Ethyl benzene
m-Xylene (1,3-Dimethyl benzene)
p-Xylene (1,4-Dimethylxylene)
Styrene (Vinyl benzene)
1,1,2,2-Tetrachloroethane
o-Xylene (1,2-Dimethyl benzene)
1, 3, 5-Tri methyl benzene (Mesitylene)
1, 2, 4-Tri methyl benzene (Pseudocumene)
m-Dichlorobenzene (1,3-Dichlorobenzene)
Benzyl chloride («-Chlorotoluene)
o-Dichlorobenzene (1,2-Dichlorobenzene)
p-Dichlorobenzene (1,4-Dichlorobenzene)
1,2,4-Trichlorobenzene
Hexachi orobut adi ene (1,1,2,3,4,4-
Hexachl oro-1 ,3-but adi ene)

FORMULA
C1CH2CH=CHC1
CH2C1CHC12
C6H5CH3
1,3-^CH3)2C6H4
1,4-(CH3)2C6H4
CHC12CHC12
1,2-(CH3)2C6H4
l,3,5-(CH3)3CeH6
1,2,4-(CH3)3C6H6
1,3-C12C6H4
1,2-C12C6H4
1,4-C12C6H4
l,2,4-Cl3CeH3


MOLECULAR
WEIGHT
110.97
133.41
92.15
187.88
165.83
112.56
mfi 17
106.17
106.17
104.16
167.85
106.17
120.20
120.20
147.01
126.59
147.01
147.01
181.45


BOILING
POINT (°C)
112.0
113.8
110,6
131.3
121.1
132.0
136 2
139.1
138.3
145.2
146.2
144.4
164.7
169.3
173.0
179.3
180.5
174.0
213.5


MELTING
POINT (°C)

-36.5
.... -95.0
9.8
-19.0
-45.6
-95.0
-47.9
13.3
-30.6
-36.0
-25.2
-44.7
-43.8
-24.7
-39.0
-17.0
53.1
17.0


CAS
\NUMBER

79-00-5
108-88-3
106-93-4
127-18-4
108-90-7
100-41-4
100-42-5
79-34-5
108-67-8
95-63-6
541-73-1
100-44-7
95-50-1
106-46-7
120-82-1


                                                                                     o
                                                                                     t—'
                                                                                     f*
                                                                                     I

-------
                     T014-62

TABLE 2.  ION/ABUNDANCE AND EXPECTED RETENTION TIME
          FOR SELECTED VOCs ANALYZED BY GC-MS-SIM
Ion/Abundance
Compound (amu/% base peak)
Freon 12 (Dichi orodi fl uoromethane)

Methyl chloride (Chloromethane)

Freon 114 (1, 2-Dichloro-l, 1,2,2-
tetrafluoroethane)

Vinyl chloride (Chloroethene)


Methyl bromide (Bromomethane)

Ethyl chloride (Chl oroethane)


Freon 11 (Trichl orof 1 uoromethane)

Vinylidene chloride (1,1-Dichloroethylene)


Dichloromethane (Methylene chloride)


Freon 113 (l,l,2-Trichloro-l,2,2-
trifluoroethane)

1,1-Dichloroethane (Ethylidene dichloride)


cis-l,2-Dichloroethylene


Chloroform (Trichloromethane)


1,2-Dichloroethane (Ethylene dichloride)


Methyl chloroform (1,1,1-Trichl oroethane)


Benzene (Cyclohexatriene)


Carbon tetrachloride (Tetrachloromethane)

85/100
87/ 31
50/100
52/ 34
85/100
135/ 56
87/ 33
62/100
27/125
64/ 32
94/100
96/ 85
64/100
29/140
27/140
101/100
103/ 67
61/100
96/ 55
63/ 31
49/100
84/ 65
86/ 45
151/100
101/140
103/ 90
63/100
27/ 64
65/ 33
61/100
96/ 60
98/ 44
83/100
85/ 65
47/ 35
62/100
27 / 70
64/ 31
97/100
99/ 64
6 If 61
78/100
77/ 25
50/ 35
117/100
119/ 97
Expected Retention
Time (min)
5.01

5.69

6.55


6.71


7.83

8.43


9.97

10.93


11.21


11.60


12.50


13.40


13.75


14.39


14.62


15.04


15.18

                                                      (continued)

-------
TABLE 2.
           T014-63

ION/ABUNDANCE AND EXPECTED RETENTION TIME  FOR
SELECTED VOCs ANALYZED BY GC-MS-SIM (cont.)
Ion/Abundance
Compound (amu/% base peak)
1,2-Dichloropropane (Propylene dichloride)


Trichloroethylene (Trichloroethene)


cis-l,3-Dichloropropene


trans-l,3-Dichloropropene (1,3
dichloro-1-propene)

1,1,2-Trichl oroethane (Vinyl trichloride)


Toluene (Methyl benzene)

1,2-Dibromoethane (Ethylene dibromide)


Tetrachl oroethylene (Perchloroethylene)


Chlorobenzene (Benzene chloride)


Ethyl benzene

m,p-Xylene(l, 3/1, 4-di methyl benzene)

Styrene (Vinyl benzene)

1 ,1 ,2 ,2-Tetrachl oroethane (Tetrachl oroethane)

o-Xylene (1,2-Dimethylbenzene)

4-Ethyltoluene

1, 3, 5-Tri methyl benzene (Mesitylene)

1,2,4-Trimethylbenzene (Pseudocumene)

m-Dichlorobenzene (1,3-Dichlorobenzene)


63/100
4 1/ 90
62/ 70
130/100
132/ 92
95/ 87
75/100
39/ 70
77/ 30
75/100
39 / 70
77/ 30
97/100
83/ 90
61/ 82
91/100
92/ 57
107/100
109/ 96
27/115
166/100
164/ 74
131/ 60
112/100
77/ 62
114/ 32
91/100
106/ 28
91/100
106/ 40
104/100
78/ 60
103/ 49
83/100
85/ 64
91/100
106/ 40
105/100
120/ 29
105/100
120/ 42
105/100
120/ 42
146/100
148/ 65
111/ 40
Estimated Retention
Time (min)
15.83


16.10


16.96


17.49


17.61


17.86

18.48


19.01


19.73


20.20

20.41

20.81

20.92

20.92

22.53

22.65

23.18

23.31


                                                   (continued)

-------
                                 T014-64
            TABLE 2.   ION/ABUNDANCE AND EXPECTED RETENTION TIME FOR
                       SELECTED VOCs ANALYZED BY GC-MS-SIM (cont.)
           Compound
 Ion/Abundance
(amu/% base peak)
Expected Retention
   Time (min)
Benzyl chloride («-Chlorotoluene)

p-Dichlorobenzene (1,4-Dichlorobenzene)


o-Dichlorobenzene (1,2-Dichlorobenzene)


1,2,4-Trichlorobenzene
Hexachlorobutadiene (1,1,2,3,4,4
  Hexachloro-1,3-butadi ene)
     91/100
    126/ 26
    146/100
    148/ 65
    111/ 40
    146/100
    148/ 65
    111/ 40
    180/100
    182/ 98
    184 / 30
    225/100
    227/ 66
    223/ 60
      23.32

      23.41


      23.88


      26.71


      27.68

-------
                                 TO14-65

             TABLE 3.   GENERAL  GC AND MS  OPERATING  CONDITIONS
Chromatography

Column
Carrier Gas
Injection Volume
Injection Mode

Temperature Program

Initial Column Temperature
Initial Hold Time
Program

Final Hold Time

Mass Spectrometer

Mass Range
Scan Time
El Condition
Mass Scan
Detector Mode

FID System (Optional)

Hydrogen Flow
Carrier Flow
Burner Air
Hewlett-Packard OV-1 crosslinked
methyl silicone (50 m x 0.31-mm I.D.,
17 urn film thickness), or equivalent

Helium (2.0 cm3/min at 250°C)
Constant (1-3 uL)
Splitless
-50°C
2 min
8°C/min to 150°C

15 min
18 to 250 amu
1 sec/scan
70 eV
Follow manufacturer's instruction for selecting
  mass selective detector (MS) and selected ion
  monitoring (SIM) mode
Multiple ion detection
 30 cm3/minute
 30 cm^/minute
400 cm^/minute

-------
                             T014-66





TABLE 4.  4-BROMOFLUOROBENZENE KEY IONS AND ION ABUNDANCE  CRITERIA







Mass                              Ion Abundance Criteria








 50                            15 to 40% of mass 95



 75                            30 to 60% of mass 95



 95                            Base Peak,  100% Relative  Abundance



 96                            5 to 9% of  mass 95



173                            <2% of mass 174



174                            >50% of mass 95



175                            5 to 9% of  mass 174



176                            >95% but< 101% of mass  174



177                            5 to 9% of  mass 176

-------
                     T014-67
TABLE 5.  RESPONSE FACTORS (ppbv/area count)  AND
          EXPECTED RETENTION TIME FOR GC-MS-SIM
          ANALYTICAL CONFIGURATION
                    Response Factor         Expected Retention
                                            Time (minutes)
lUliipuunua 	 	 	
Freon 12
Methyl chloride
Freon 114
Vinyl chloride
Methyl bromide
Ethyl chloride
Freon 11
Vinylidene chloride
Dichloromethane
Trichlorotrifluoroethane
1,1-Dichloroethane
cis-l,2-Dichloroethylene
Chloroform
1,2-Dichloroethane
Methyl chloroform
Benzene
Carbon tetrachloride
1,2-Dichloropropane
Trichloroethylene
ci s-1 ,3-Dichl oropropene
trans-l,3-Dichloropropene
1,1,2-Trichloroethane
Toluene
1,2-Dibromoethane (EDB)
Tetrachloroethylene
Chlorobenzene
Ethyl benzene
m,p-Xylene
Styrene
1 ,1 ,2 ,2-Tetrachl oroethane
o-Xylene
4-Ethyltoluene
1 , 3, 5-Tri methyl benzene
1 ,2 ,4-Tri methyl benzene
m-Dichlorobenzene
Benzyl chloride
p-Dichlorobenzene
o-Dichlorobenzene
1,2,4-Trichlorobenzene
Hexachlorobutadiene
0.6705
4.093
0.4928
2.343
2.647
2.954
0.5145
1.037
2.255
0.9031
1.273
1.363
0.7911
1.017
0.7078
1.236
0.5880
2.400
1.383
1.877
1.338
1.891
0.9406
0.8662
0.7357
0.8558
0.6243
0.7367
1.888
1.035
0.7498
0.6181
0.7088
0.7536
0.9643
1.420
0.8912
1.004
2.150
0.4117
5.01
5.64
6.55
6.71
7.83
8 A O
.43
9.87
10.93
11.21
11.60
i n c f\
12.50
13.40
1*5 "I C
13.75
14.39
14.62
15.04
15.18
15.83
1C 1 f\
16.10
1C f\C
16.96
UA rt
.49
Uf -m
.61
17.86
18.48
19.01
1 f\ TO
19.73
20.20
20.41
o r\ on
Zu.oO
20.92
20.92
22.53
22.65
f\f\ 10
23.18
23.31
23.32
23.41
oo o o
23.88
26.71
27.68

-------
                                     T014-68
                     TABLE  6.   GC-MS-SIM  CALIBRATION  TABLE
                           *** External  Standard   *•**
Operator: JDP
Sample In-fc :
Misc In-fo:
Integration Fi1
SYR 1
   Name :  DATA:SYR2A02A.I
      Sequence Index: 1
                                                 8  Jan  87   10:02
                                           Bottle  Number  :  2
                          Last Update:  8 Jan  87    8: 13  am
                Re-ference Peak Window:    5.00 Absolute  Minutes
            Non-Re-ference Peak Windows    O.40 Absolute  Minutes
Sample Amount: O.OOO  Uncalibrated Peak RF: 0.000   Multiplier:  1.667

                                            Compound
                                               Name
                                            FREON 12
                                            METHYLCHLORI
                                            FREON 114
                                            VINYLCHLORID
                                            METHYLBROMID
                                            ETHYLCHLORID
                                            FREON 11
                                            VINDENECHLOR
                                            DICHLOROMETH
                                            ALLYLCHLORID
                                            3CHL3FLUETHA
                                            1,1DICHLOETH
                                            c-l,2DICHLET
                                            CHLOROFORM
                                            1,2DICHLETHA
                                            METHCHLOROFO
                                            BENZENE
                                            CARBONTETRAC
                                            1,2DICHLPROP
                                            TRICHLETHENE
                                            c-l,3DICHLPR
                                            t-l,3DICHLPR
                                            1,1,2CHLETHA
                                            TOLUENE
                                            EDB
                                            TETRACHLETHE
                                            CHLOROBENZEN
                                            ETHYLBENZENE
                                            m,p-XYLENE
                                            STYRENE
                                            TETRACHLETHA
                                            o-XYLENE
                                            4-ETHYLTOLUE
                                            1,3,5METHBEN
                                            1,2,4METHBEN
                                            m-DICHLBENZE
                                            BENZYLCHLORI
                                            p-DICHLBENZE
                                            o-DICHLBENZE
                                            1,2,4CHLBENZ
                                            HEXACHLBUTAD
Ret
Ti me
• 5.020
5.654
6.525
6 . 650
7.818
8.421
9. 940
10.369
11. 187
1 1 . 225
1 1 . 578
12.492
13.394
13.713
14.378
14.594
1-5. OO9
15. 154
15.821
16.067
16.941
17.475
17.594
17.844
18.463
1 8 . 989
19.705
20. 168
20.372
20.778
20.887
20.892
22.488
22.609
23. 144
23.273
23.279
23.378
23.850
26.673
~*~7 i"1*""*
4. 1 m Ow' /
Si gnal
Descripti on
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
85.
50.
85.
62.
94.
64.
101.
61.
49.
41.
151.
63.
61.
83.
62.
97.
78.
117.
63.
130.
75.
75.
97.
91.
107.
166.
112.
91.
91.
1 04 .
83.
91.
105.
1 05 .
105.
146.
91.
146.
146.
1 80 .
225.
00 amu
OO amu
OO amu
OO amu
OO amu
OO amu
00 amu
OO amu
OO amu
OO amu
00 amu
00 amu
OO amu
OO amu
OO .amu
OO amu
OO amu
OO amu
OO amu
OO amu
OO amu
OO amu
OO amu
OO amu
00 amu
OO amu
OO amu
OO amu
00 amu
00 amu
00 amu
00 amu
OO amu
OO amu
OO amu
OO amu
00 amu
OO amu
00 amu
OO amu
00 amu
Area
12893
4445
7067
2892
2401
2134
25069
5034
4803
761
5477
5O52
4761
.5327
5OO9
6656
8352
5888
3283
4386
2228
1626
2721
14417
4070
6874
5648
11084
17989
3145
4531
9798
7694
6781
7892
3046
3880
6090
2896
562
63O9
Amount
4011 pptv
2586 pptv
1215 pptv
1929 pptv
1729 pptv
2769 pptv
6460 pptv
1700 pptv
2348 pptv
8247 pptv
1672 pptv
1733 pptv
1970 pptv
1673 pptv
2263 pptv
2334 pptv
2167 pptv
1915 pptv
179r pptv
2109 pptv
987.3 pptv
689.2 pptv
1772 pptv
2733 pptv
1365 pptv
2065 pptv
1524 pptv
1842 pptv
3790 pptv
1695 pptv
1376 pptv
2010 pptv
1481 pptv
1705 pptv
2095 pptv
1119 pptv
1006 pptv
2164 pptv
1249 pptv
767. 1 pptv
1789 pptv




.j.

*



*

*






*





*•

















-------
                              T014-69

             TABLE 7.  TYPICAL RETENTION TIME (MIN) AND
           CALIBRATION RESPONSE FACTORS (ppbv/area count)
               FOR TARGETED VOCs ASSOCIATED WITH FID
                     AND ECD ANALYTICAL SYSTEM


Peak
Number1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 x
29
30
31
32
33
34
35
36
37
38
39
40


Compound
rreon 12
Methyl chloride
Freon 114
Vinyl chloride
Methyl bromide
Ethyl chloride
Freon 11
Vinylidene chloride
Dichloromethane
Trichlorotrifluoroethane
1,1-Dichloroethane
ci s-l,2-Dichloroethylene
Chloroform
1,2-Dichl oroethane
Methyl chloroform
Benzene
Carbon tetrachloride
1,2-Dichl oropropane
Trichloroethylene
ci s-l,3-Dichloropropene
trans-l,3-Dichloropropene
1 ,1 ,2-Trichl oroethane
Toluene
1,2-Dibromoethane (EDB)
Tetrachl oroethylene
Chlorobenzene
Ethyl benzene
m,p-Xylene
Styrene
1 ,1 ,2 ,2-Tetrachl oroethane
o-Xylene
4-Ethyltoluene
1, 3, 5-Tri methyl benzene
1 ,2, 4-Tri methyl benzene
m-Dichlorobenzene
Benzyl chloride
p-Dichlorobenzene
o-Dichlorobenzene
1 ,2 ,4-Trichl orobenzene
Hexachlorobutadiene


detention
Time (RT) ,
minutes
3.65
4.30
5.13
5.28
6.44
7.06
8.60
9.51
9.84
10.22
11.10
11.99
12.30
12.92
13.12
13.51
13.64
14.26
14.50
15.31
15.83
15.93
16.17
16.78
17.31
18.03
18.51
18.72
19.12
19.20
19.23
20.82
20.94
21.46
21.50
21.56
21.67
22.12
24.88
25.82
FID T
Response 1
Factor (RF)
(ppbv/area
count)
3.465
0.693
0.578
0.406

0.413
6.367
0.347
Of\ f\ ^
.903
0.374
0.359
0.368
1.059
0.409
0.325
0.117
1.451
0.214
0.327


0.336
0.092
0.366
0.324
0.120
0.092
0.095
0*1 fl O
.143

01 rt f\
.100
0.109
0.111


0.188
0.188
0.667
0.305
ECD
Response
-actor
(ppbv/area
count x 10~b)
13.89
22.32
f\f *) A
26.34

1.367


3.955

U*l A
.14

3.258

1.077
8.910




5.137
1.449




9.856








1.055
1 Refer to Figures 15 and 16 for peak location

-------
                          T014-70

       TABLE 8.  TYPICAL RETENTION TIME (minutes) FOR
                 SELECTED OR6ANICS USING GC-FID-ECD-PID*
                 ANALYTICAL SYSTEM
Compound
Acetylene
1,3-Butadiene
Vinyl chloride
Chloromethane
Chi oroethane
Bromoethane
Methylene Chloride
trans-l,2-Dichloroethylene
1,1-Dichl oroethane
Chloroprene
Perfluorobenzene
Bromo chloromethane
Chloroform
1,1,1-Trichl oroethane
Carbon Tetrachloride
Benzene/1 ,2-Dichl oroethane
Perfluorotoluene
Trichloroethylene
1,2-Dichloropropene
Bromodichloromethane
trans -1,3-Dichloropropylene
Toluene
ci s-1 ,3-Dichl oropropylene
1,1,2-Trichloroethane
Tetrachloroethylene
Dibromo chloromethane
Chlorobenzene
m/p-Xylene
Styrene/o-Xylene
Bromofluorobenzene
1,1,2,2-Tetrachloroethane
m-Dichlorobenzene
p-Dichlorobenzene
o-Dichlorobenzene
Retention Time minutes)
FID
2.984
3.599
3.790
5.137
5.738
8.154
9.232
10.077
11.190
11.502
13.077
13.397
13.768
14.151
14.642
15.128
15.420
17.022
17.491
18.369
19.694
20.658
21.461
21.823
22.340
22.955
24.866
25.763
27.036
28.665
29.225
32.347
32.671
33.885
ECD


__
__



•» M
W «
__
13.078
13.396
13.767
14.153
14.667

15.425
17.024
17.805

19.693
•» *»
21.357

22.346
22.959


	
28.663
29.227
32.345
32.669
33.883
PIP

3 594
*J • -J J"
3 781
+r • / "— *JL


9 218
•J • t_ Xw
10.065

11 491
•*• J- • i -• J.
13.069
13.403
13.771
14 158
±~ + ± *j \j
14.686
15 114
* *J • J. X *
15 41?
J. *J • T^ X t.
17 014
* r • w X ~
17 522
JL / « v/ L. 4.
19.688
20.653
21.357

22.335
22.952
?4 ftfil
t.1* .001
25 757
(~ -J + 1 %/ /
27.030
28.660
29.228
32.342
32.666
33.880
Varian® 3700 GC equipped with J & W Megabore® DB 624 Capillary
Column (30 m X 0.53 I.D. mm) using helium carrier gas.

-------
                                    T014-71

                      TABLE 9.   GC-MS-SIM CALIBRATION TABLE
                          Last Updates  IB  Dec  86   7:54 am
                Re-ference Peak Window:     5.OO Absolute Minutes
            Non-Re-ference Peak Window:     0.40 Absolute Minutes
Sample Amount: O.OOO  Uncalibrated Peak RF:  O.OOO  Multiplier:  l.OOO
Ret Time Pk#
5.008
5.690
6.552
6.709
7.831
8.431
9 . 970
10.927
1 1 . 209
11.331
11.595
12.502
13.403
13.747
1 4 . 337
14.623
-J5.038
•15.133
15.829
16.096
16.956
17.492
17.610
17.362
13.485
19.012
19.729
2O. 195
20.407
2O. 306
20.916
2O. 921
22.523
22.648
23. 179
23.3O7
23.317
23.413
23.335
26.714
27.680
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
IS
19
20
21
22
23
24
25
26
27
23
29
3O
31
32
33
34
35
36
37
33
39
40
41
Signal Descr Amt pptv
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
85 . 00 amu
SO. 00 amu
35.00 amu
62.00 amu
94.00 amu
64.00 amu
101. OO amu
61.0O amu
49.0O amu
4 1 . OO amu
151. OO amu
63. OO amu
6 1 . 00 amu
83. OO amu
62 . OO amu
97 . 00 amu
73.00 amu
117.00 amu
63 . 00 amu
130.00 amu
75.OO amu
75 . OO amu
97 . 00 amu
9 1 . 00 amu
107.00 amu
1 66 . OO amu
112. OO amu
9 1 . OO amu
9 1 . 00 amu
1 O4 . 00 amu
33 . OO amu
9 1 . OO amu
105.0O amu
1O5.OO amu
1 05 . OO amu
146.OO amu
9 1 . 00 amu
146.OO amu
146.OO amu
1 BO . OO amu
225 . OO amu
13620
12720
8380
3050
12210
12574
1238O
7890
1276O
12650
7420
12710
12630
7670
904O
810O
1076O
3340
1273O
8750
454O
338O
12690
10O1O
6710
783O
716O
1274O
254OO
1239O
1169O
1 1 085
1256O
1262O
1271O
1265O
7900
1239O
1351O
1552O
747O
Lvl CArea]
1 72974
1 36447
1 81251
1 20118
1 28265
1 16149
1 8O088
1 38954
1 43507
1 1945
1 40530
1 61595
1 509OO
1 4O585
1 33356
1 33503
1 69119
1 42737
1 33375
1 30331
1 . 17078.
1 13294
1 32480
1 8BO36
1 3335O
1 43454
1 44224
1 127767
1 200973
1 38332
1 64162
1 9OO96
1 108747
1 83666
1 79333
1 574O9
1 50774
1 58127
1 52233
1 18967
1 43920
                                                           Pk-Type  .Partial Name
                                                                 1 FRECIM 12
                                                                 1 ItETHYLCHLQRID
                                                                 1 FREDN 114
                                                                 1 VINYLCHLORIDE
                                                                 1 METHYLBROMIDE
                                                                 1 ETHYLCHLORIDE
                                                                 1 FREON 11
                                                                 1 VINDENECHLORi
                                                                 1 DICHLOROMETHA
                                                                 1 ALLYLCHLORIDE
                                                                 1 3CHL3FLUETHAN
                                                                 1  1,1DICHLCETHH
                                                                 1 c-l,2DICHLETH
                                                                 1 CHLOROFORM
                                                                 1  1.2DICHLETHAN
                                                                 1 METHCHLORCFOR
                                                                 1  BENZENE
                                                                 1 CARBCNTETRACH
                                                                 1  1.2DTCHLFRCPA
                                                                 1  TRICHLETHENE
                                                                 1  c-i,3DICHl.PRO
                                                                 1  t-l,3DICHLPRC
                                                                 1  1 , 1,2CHLE7HAN
                                                                 1  TOLUENE
                                                                 1  EDB
                                                                 1  TETRACKLETMEN
                                                                  1  CHLQRGBENZENE
                                                                  1  ETHYLBENZE^4E
                                                                  1  m,p~XYLENE
                                                                  1  STYRENE
                                                                  1  TETRACHLETHAN.
                                                                  1  o-XYLENE
                                                                  1  4-ETHYLTOLUEN
                                                                  1  1,3,SMETHBENZ
                                                                  1  1,2,4METHBENZ
                                                                  1  m-DICHLBEN2EN
                                                                  1  BENZYLCHLCRID
                                                                  1  p-DICHLBEHZEN
                                                                  1  o-DICHLBENZEN
                                                                  1  1,2,4CHLBENZE
                                                                  1  HEXACHLBUTADI

-------
                      T014-72
   TABLE 10. EXAMPLE OF HARD-COPY OF GC-MS-SIM ANALYSIS
 Data  -file:  DATA: SYR2A02A. D
 File  type:  GC / MS DATA  FILE

 Name  In-fo:  SYR 1
 Mi sc  In-fo:
 Operator  :  JDP
 Date      :   8 Jan 37
 Instrment:  MS_5970
 Inlet     :  GC

 Sequence index; :     1
 Als bottle  num :     2
 Replicate num  :     1
                         10:02 am
    TIC  af  DRTR.-EVR3RD2R.D
   IBQCl


   1EBB

   14BB




   1BBB

    BOB


    BBB'
    2BB-

      tj.
                  IB
                          15
2Q
25
                                                    3Q
       ***  integration Parameters ***

FALSE  : Shoulder Detection Enabled
0.020  : Expected Peak Width  
-------
                                 T014-73
       TABLE 10.  EXAMPLE OF HARD-COPY OF GC-MS-SIM ANALYSIS (cont.)
Operator: JDP
Sample In-fc : SYR 1
Misc In-fo:
Integration File Name i DATA:SYR2A02A. I
                    Sequence Index: 1
                                                              8 Jan 87  10:02 *»•
Bottle Number t 2
                          Last Update:  8 Jan 87   6: 13 am
                Re-ference Peak Window:    5.00 Absolute Minutes
            Non-Re-ference Peak Window:    0.40 Absolute Minutes
Sample Amount: 0.000  Uncalibrated Peak RF:  0.000  Multiplier:  1.667

                                             Compound
                                              Name
                                        amu  FREON  12
                                        amu  METHYLCHLOR1
                                        amu  FREON  114
                                        amu  VINYLCHLORID
                                        amu  METHYLBROMID
                                        amu  ETHYLCHLORID
                                        amu  FREON  11
                                        amu  VINDENECHLOR
                                        amu  DICHLOROMETH
                                        amu  ALLYLCHLORID
                                         amu  3CHL3FLUETHA
                                         amu  1,1DICHLOETH
                                         amu  c-l,2DICHLET
                                         amu  CHLOROFORM
                                        .amu  1,2DICHLETHA
                                         amu  METHCHLOROFD
                                         amu BENZENE
                                         amu CARBONTETRAC
                                         amu 1,2DICHLPROP
                                         amu TRICHLETHENE
                                         amu c-l,3DICHLPR
                                         amu t-l,3DICHLPR
                                         amu 1,1,2CHLETHA
                                         amu TOLUENE
                                         amu EDB
                                         amu TETRACHLETHE
                                        -amu CHLOROBENZEN
                                         amu ETHYLBENZENE
                                         amu m,p-XYLENE
                                         amu STYRENE
                                         amu TETRACHLETHA
                                         amu o-XYLENE
                                         amu 4-ETHYLTOLUE
                                         amu 1,3,5METHBEN
                                         amu 1,2,4METHBEN
                                         amu m-DICHLBENZE
                                         amu BENZYLCHLORI
                                         amu p-DICHLBENZE
                                         amu o-DICHLBENZE
                                         amu 1,2,4CHLBENZ
                                         amu HEXACHLBUTAD
Peal:.
Num Type
1
2

A
C"(
6
"T
/
8
«?
«*!
i
• »*i
j, *^
1 T,
1-
15
\ e
•7
13
1s?
20
21
/•%*".
^•'~.
2*
*•>«•
«» *•'
26
27
25
'?
30
31
*Tt~,
W «
33
34
3S
5
37
3S
39
40
41
Int
Type
1 PP '
1 PP
] BP
1 PB
1 BP
1 BB
1 BV
1 BP
1 BP
1 PP
1 BP
1 BP
3 VP
1 PH
1 BP
1 PB
1 VP
1. VP
1 BB
1 BB
1 PB
1 BP
1 BB
1 BV
1 PB
1 PH
1 PB
1 BP
1 PB
1 BV
1 BH
1 BP
1 W
1 VB
1 BB
1 BV
1 VV
1 VB
1 BP
1 BB
1 BB
Ret
Time
5.020
5.654
6.525
6 . 650
7. BIB
8.421
9.940
10.369
11.187
1 1 . 225
1 1 . 578
12.492
13.394
13.713
14.378
14.594
V5.O09
15. 154
15.821
16.067
16.941
17.475
17.594
17.844
18.463
18.989
19.705
20. 16B
20.372
20.778
20.887
20.892
22.488
22.609
23. 144
23.273
23.279
23.378
23. 850
26.673
27.637
Si
gnal
Descripti on
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
B5.OO £
50.00 c
85.00 i
62. OO i
94.00 c
64.00 i
101.00 •
61.00 i
49.00 i
41.00 i
151.00 i
63.00 •
61.OO •
•83.00 .
62.00 .,
97.00 .
78.00 .
117.OO
63.00
130.00
75.00
75.00
97 . 00
91.00
1 07 . OO
1 66 . OO
112.OO-
9 1 . OO
91.OO
1 04 . OO
83 . 00
91.00
105.00
105.00
105.00
146.00
91.00
146.00
146.00
180.00
Mass 225.00
Area
12893
4445
7067
2892
2401
2134
25069
5034
4803
761
5477
5052
4761
.5327
5009
6656
8352
58BB
32B3
4386
222B
1626
2721
14417
4070
6B74
5648
11084
17989
3145
4531
9798
7694
67S1
7892
3046
3880
609O
2896
562
6309
Amount
4011 pptv
2586 pptv
1215 pptv
1929 pptv *
1729 pptv
2769 pptv +
6460 ppt\
1700 pptv
2343 pptv
8247 pptv *
1672 pptv
1738 pptv *
1970 pptv
1673 pptv
2263 pptv
2334 pptv
2167 pptv
1915 pptv
1799 pptv *
2109 pptv
987.3 pptv
689.2 pptv
1772 pptv
2733 pptv
1365 pptv *•
2065 pptv
1524 pptv
1842 pptv
3790 pptv
1695 pptv
1376 pptv
2010 pptv
1481 pptv
1705 pptv
2095 pptv
1119 pptv
1006 pptv
2164 pptv
1249 pptv
767. 1 pptv
1789 pptv

-------
      GC-MS-SCAN
     (Section 10.4.2)
                                   T014-74
                                Receive
                                Sample
                                Canister
                                (Section
                                 9.2.2)
                              Log Sample In
                            (Section 10.4.1.2)
                            Check and Record
                              initial Pressure
                            (Section 10.4.1.3)
                                Analyze
                 <83kPa
                 (12psig).
                (Optional)
  GC-MS-SIM
(Section 10.4.3)
       Pressurize
       with N2 To
        138 kPa
        (20pslg)
                                                          Record Final
                                                            Pressure
                                                        (Section 10.4.1.3)
                              Calculate
                            Dilution Factor
                          (Section 10.4.1.4)
 GC-Multldetector
(GC-FID-ECD-PID)
 (Section 10.4.4)
             Non-Specific Detector (FID)
                    (Optional)
FIGURE 1.   ANALYTICAL SYSTEMS AVAILABLE  FOR CANISTER
              VOC IDENTIFICATION AND QUANTITATION

-------
Inlet
~1.6 Meters
  (-5 ft)
     1
     Ground
     Level
  Vent
                                       T014-75


                                      To AC
                  Insulated Enclosure
                  Inlet
                Manifold
                                     M M
                         Vacuum/Pressure
                             Gauae
                                  Electronic
                                   Time