United States                      EPA-340/1-80-010
Environmental Protection  Office of General Enforcement    March 1980
Agency         Washington DC 20460

Stationary Source Enforcement Series	



Summary of Available


Portable  VOC


Detection Instruments

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                            EPA-340/1-80-010
Summary of Available
      Portable VOC
Detection Instruments
               by

     Mazen Y Anastas. Herbert J. Belknap

        PEDCo Environmental, Inc.
       1006 N. Bowen Road. Suite 201
          Arlington. TX 76012
         Contract No. 68-01-4147
            Task No 120


      EPA Project Officer: John R. Busik




             Prepared for

   U.S ENVIRONMENTAL PROTECTION AGENCY
       Office of General Enforcement
    Division of Stationary Source Enforcement
         Washington. DC 20460

             March 1980

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                           DISCLAIMER


     This report was  furnished  to  the U.S.  Environmental Protec-
tion  Agency  by PEDCo  Environmental,  Inc.,   in  fulfillment  of
Contract No.  68-01-4147.  The contents  of this report are repro-
duced  herein as  received  from the  contractor.   The  opinions,
findings, and conclusions expressed are those of the author and
not necessarily those of  the  U.S.  Environmental Protection Agen-
cy.  Mention  of company or  product names is not to be considered
as  an  endorsement by the Environmental Protection  Agency.   All
costs are in fourth quarter 1979 dollars.
                                11

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                            CONTENTS
Tables                                                        iv
Acknowledgment                                                 v

1    Introduction and Summary                                  1

     Background                                                1
     Summary of Findings                                       2

2    Measurement Of VOC                                        5

     Introduction                                              5
     Reference Methods                                         5
     Types Of VOC Detectors                                    7
     References                                               10

3    Portable VOC Instruments                                 12

     Performance Characteristics                              12
     Survey of Instrument Manufacturers                       12
     Survey Results                                           22

4    Conclusions and Recommendation                           27

     lonization Detectors                                     27
     Infrared Detectors                                       28
     Combustibles Analyzers                                   29
     Miscellaneous Instruments                                29
     Development Plans                                        29

Appendix - Sources Of VOC                                    A-l
                               111

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                             TABLES

Number                                                       Page
   1      Instrument Parameters                                13
   2      Portable lonization Detectors                        15
   3      Portable Infrared Instruments                        18
   4      Portable Combustibles Analyzers                      20
                                IV

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                         ACKNOWLEDGMENT
     This   report   was  prepared   under   the   direction   of
Thomas C. Ponder, Jr.  The project was  managed by Mazen Y.  Anastas
The    principal    investigators   were   Mazen  Y. Anastas    and
Herbert J. Belknap.   Task  Manager  for  the  U.S.  Environmental
Protection Agency was Mr. Robert L.  King.

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                            SECTION 1
                    INTRODUCTION AND SUMMARY

BACKGROUND
     The U.S.  Environmental Protection  Agency (EPA) has  issued
control techniques guidelines  (CTG)  for  a number of sources that
emit volatile organic compounds  (VOC).   These guidelines concern
industries that emit significant  quantities  of air pollutants in
oxidant  nonattainment   areas   for  National  Ambient Air  Quality
Standards  (NAAQS).   The industries  and  appropriate controls are
discussed in the Appendix.
     Control methodologies described in these documents represent
reasonably  available  control  technology  (RACT)  that can  be ap-
plied to existing  sources.   The definition of RACT is the lowest
emission limit  that a particular  source  can meet by application
of control  technology  that is  reasonably available, considering
technological and  economic feasibility.   Thus,  RACT may require
technology that has  been applied to similar, but not necessarily
identical,  source  categories.  The  intention is not  to require
extensive research and development before a given control techno-
logy  can  be  applied  to  the  source.   This does  not,  however,
preclude requiring  a short-term evaluation program to permit the
application of a given technology to a particular source; such an
effort is an appropriate technology  forcing aspect of RACT.
     For  many  VOC  sources,   the control  technologies must be
implemented by  January  1,  1982.   This implies the monitoring of
compliance  of many  sources.   In  doing   so,  Federal,  state, and
local  enforcement  agencies will  require accurate,  portable, and
relatively  inexpensive  instruments  and  methods  to  determine
compliance.

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     Depending on  the  industry,  VOC emissions may include single
compounds  or mixtures  of  compounds.    In  the  latter case,  an
effective measurement method  is  difficult to determine.  Because
of  the  large number of organic compounds or  species  that may be
present in a given emission (gasoline vapors are a good example),
determining  individual  compounds is difficult  and  costly.   As a
result, EPA  has  adopted Reference  Method 25,  which measures the
organic carbon content  of  VOC emissions.  Total gaseous nonmeth-
ane  organic  compounds  (TGNMO)  are measured  by  (1)  removal  of
methane,  carbon  dioxide,   and carbon monoxide  from  the  sample,
(2) combustion of  organic  compounds to  carbon dioxide, (3) con-
version of the carbon  dioxide to methane, and (4) measurement in
a flame ionization detector (FID).
     The  cost of  equipment   to  perform  Method  25   is  between
$10,000 and $20,000, and the method requires well trained person-
nel  for  operation and maintenance.  The  EPA  recognizes that for
certain  sources  "alternative"  or  "screening"  methods  may  be
available  in lieu  of  Method 25  for compliance  determinations.
     Under Contract No. 68-01-4147,  Task  120,  the  Division  of
Stationary Source Enforcement (DSSE), U.S.  EPA,  authorized PEDCo
Environmental,  Inc.,  to conduct  a  survey to  investigate current
instruments  available  for  field-screening VOC  emissions.   PEDCo
investigated the availability of accurate, relatively inexpensive
portable  instruments  and  methods of measuring  VOC.   This report
presents the information gathered on performance characteristics
of  these  instruments  and the  plans  reported  for  future develop-
ment to  reduce  instrument costs  and widen the  applicability of
instruments.

SUMMARY OF FINDINGS
     PEDCo conducted  a  survey  of  instrument manufacturers  and
obtained  information on the  cost,  weight,  and  performance char-
acteristics of various  instruments.   Four categories  of portable
instruments,  classified by  principle of  operation,  are ionization

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detectors,  infrared  detectors,  combustibles analyzers,  and  mis-
cellaneous instruments.
     Most of  the  instruments identified in this  survey  are  cur-
rently  used  to  detect  process  leaks.  With  relatively  minor
modifications,  however,  many of these  instruments  could be  used
for  determining compliance.  Some  care should  be exercised  to
select instruments compatible with the particular constituents of
the  exhaust  gas  stream.   The  FID's  use  a method   similar  to
Method 25. '
     It  is  possible  that  none of  these  instruments would  be
compatible with emissions  whose chemical composition fluctuates
greatly or is unknown.   When all components are known, gas chro-
matograph (GC)  separation  facilitates  measuring  individual  com-
ponent concentrations.
     The portable ionization detectors, notably  FID's,  are ver-
satile, accurate, and highly sensitive.  The FID's detect organic
carbon  and  are recommended  for Method 25  determinations.  Costs
of  currently  available models  range  from $2300  to $5000.  Ioni-
zation  detectors  manufactured by HNU Systems,  Inc.,  and Century
Systems can  be widely applied  for  detection of  leaks from such
sources as petroleum refineries and organic chemical manufactur-
ing  plants;  these models  sell  for  about $3500  with $1000 addi-
tional  for a  GC option.  Analytical Instrument Development, Inc.,
also  manufactures FID instruments,  which are less portable and
slightly more expensive.
     Portable infrared (IR)  instruments may be used in the deter-
mination  of  single  components  or  hydrocarbon  mixtures  such as
gasoline and  naphtha.  The determination of mixtures  depends upon
the  incorporation of multiwavelength capability into  instruments
and  the  full  characterization  of  components   emitted by  the
source.   The  costs  of available infrared  instruments range from
$1250  to  $6600.   The  less expensive  instruments  are usually
preset  to measure one species  only.   The  more expensive devices
have  a  built-in capability  for continuous variation  of  the wave-
length  in the IR  spectrum.

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      Combustibles  analyzers,  as  the  name implies,  measure the
 concentration  of combustible organic  compounds  in air as a per-
 centage  of the  lower explosive limit  (LEL).   They are currently
 used  in leak  detection and  industrial  safety  applications and
 cost  from  $160 to $1200.  The more expensive instruments are more
 accurate in  ranges from 0  to 100 ppm and  0  to  1000 ppm.  Their
 use for  monitoring  compliance activities will be  limited to leak
 detection.
     A  few. instruments  in  the miscellaneous  category should be
 studied.   Two  instruments  of potential use in industries involv-
 ing halogenated  hydrocarbons  (such  as  degreasers  and  drycleaning
 systems) are  a halide detector and  an alarm  manufactured by Gas
 Tech.   The halide detector  can measure  concentrations in ranges
 from  0 to  100  ppm and 0 to 1000 ppm and costs $1125.  The alarm,
 which  costs  about  $400,  can be preset to  "sound-off"  at any
 concentration from 0 to 100 ppm.
     Detector  tubes to  measure  specific  organic  compounds are
 available  at a cost of  $1  to $3 each.   They are used  in conjunc-
 tion  with  a  pump,  which meters a specified volume of gas sample
 and costs  about  $200.   The accuracy, precision,  and range of the
 detector tubes have not been established.
     The survey of manufacturer development plans to reduce costs
 or widen the application range of  instruments  found  that manu-
 facturers  would  rather  respond to changes  in demand for instru-
ments  than anticipate  them.  Also,   a  tenfold increase in demand
would  reduce costs by only 10 to 15  percent.

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                            SECTION 2
                       MEASUREMENT OF VOC

INTRODUCTION
     This  section  discusses  acceptable  EPA and  other  reference
methods for VOC  emission  measurement and outlines the principles
of operation of  various VOC detectors.   No instrument applicable
to all  sources combines the  desired  features  of  accuracy,  quick
response, portability, and low cost.
     Most  rules  concerning  VOC  emissions  either regulate  the
volatile organic content  of solvents or limit the exhaust volume
or mass concentrations, mass emission rates, or control equipment
efficiencies.
     In many cases total organic carbon must be used as a measure
of VOC  emissions,  because no detector responds quantitatively to
the  total  molecular structure  of  the mixture.  Although several
detectors  respond  to organic  compounds,  their response may vary
widely  from compound to compound  and may  not be  proportional to
the total organic mass or volume in a mixture.

REFERENCE METHODS
     Several  reference methods  for the  determination  of single
components  or TGNMO in emissions are described below.
Reference Method 25
     Reference  Method 25  measures TGNMO  as organic carbon.1  It
requires the  separation  of nonmethane organics from other carbon
compounds,  combustion of organics  to carbon dioxide, conversion
of carbon  dioxide  to methane, and analysis of methane by a flame
ionization  detector.  This method  has been  employed in

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Los Angeles County for many years and is considered valid and  ef-

fective for compliance determinations.2

     The performance  characteristics of  Method 25  are  as fol-

lows:3

          Accuracy:   ± 10 percent
          Precision:   ± 5 percent
          Minimum detectable concentration:   10 ppm
          Range:  10  ppm to 2 percent by volume
          Portability:  Sampling apparatus is portable;  sample
                        must be analyzed in laboratory
          Equipment cost:  $20,000

     A commercially  available instrument for  the  measurement of

TGNMO by Method 25 is  manufactured  by Byron  Instruments,  Inc.,

Raleigh,  North Carolina.4   The  Model  401  hydrocarbon  analyzer

chromatographically isolates TGNMO from methane, carbon monoxide,

and carbon dioxide;   oxidizes TGNMO  to carbon dioxide;  reduces

carbon dioxide  to methane;  and  measures  the methane  in an FID.

The estimated performance  characteristics  of this  instrument are

as follows:3'4

          Accuracy:  Unknown
          Precision:   ± 2 percent
          Minimum detectable concentration:  1 ppm
          Range:  1 ppm to 5 percent
          Response time:  10 min
          Portability:  Semiportable at 60 Ib
          Cost:  $10,000

Other Reference Methods

     Other  EPA reference  methods  can  detect  and  measure some

organic species.  The EPA test methods  for vinyl chloride (Method

106) and benzene  (Method 110) have been published.  A New Source

Performance  Standards  test  method  (Method 23) for halogenated

compounds   (perchloroethylene,   carbon   tetrachloride,   ethylene
dichloride,  trichloroethylene,  methylene chloride,  1,1,1-trich-

loroethane, and trichlorotrifluoroethane)  has also been publish-

ed.  All  these methods  involve  collection of  a  gas sample con-

taining  VOC  in a plastic  bag.   The  VOC  concentration  in  the

sample is determined by gas chromatograph with  an FID.

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TYPES OF VOC DETECTORS
     The U.S. EPA recognizes that alternative methods may be used
in lieu  of reference methods for determination of  compliance  by
certain sources.  For example,  an FID may be used where a single
component  is present.   Screening methods  may also  be used  in
certain situations  despite  their lack of precision.  A hot wire
detector,  although  not  precise, can  find gross leaks.   The fol-
lowing types of VOC detectors are discussed:
     Flame ionization detector
     Photoionization (ultraviolet)  detector
     Nondispersive infrared detector
     Thermal conductivity detector
     Hot wire detector
Flame Ionization Detector
     In an FID,  the sample  is introduced into a hydrogen flame.5
The combination of even 0.1 ppm of a hydrocarbon produces measur-
able ionization, which is a function of the number of carbon ions
present.  A positively charged collector surrounds the flame, and
the  ion  current between the flame and the  collector is measured
electronically.   Pure  hydrogen burning in  air  produces  very
little ionization,  so background effects  are essentially masked
by the hydrogen flame.   The calibrated output current is read on
a panel meter or chart recorder.
     Organic  compounds  containing nitrogen,  oxygen, or halogen
atoms give a reduced response.  The FID hydrocarbon analyzers are
usually  calibrated  in terms of a gas such  as methane or hexane,
and the output  is read in parts per million of carbon measured as
methane or hexane.
     Although  nitrogen (N2),  carbon monoxide (CO),  and  carbon
dioxide  (C02) do not produce interferences, FID's show a very low
sensitivity  to  water vapor (H20).   Condensed  water  vapor can
block  the sample entry  tube and cause  erratic  readings.   Also,
when  oxygen  exceeds  4 percent,  a   significantly   lower  output
reading  can   occur.   The relative response of the FID to various

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organic  compounds,  including  those  with attached  oxygen,  chlo-
rine,  and nitrogen  atoms,  varies from  compound to  compound.

Photoionization Detector
     Photoionization  is  the  process  where  ultraviolet  light
ionizes a molecule  as  follows:   R + hv/ •» R  + e~ where R  is the
ionized species and  hv  represents a  photon with energy less than
or  equal  to  the  ionization potential  of  the molecule.6   All
species with an ionization  potential  less than 10 electron volts
(eV) are detected.  Because the ionization potential of all major
components of air  [oxygen  (02),  N2,  CO,  C02, and H20] is greater
than 10 eV,  they are not detected.
     The  sensor  consists  of  an argon-filled,  ultraviolet  (UV)
light  source  that  emits  photons.   A  chamber  adjacent to  the
sensor contains a pair  of  electrodes.   When a positive potential
is  applied  to  one electrode,  the field created  drives  any ions
formed by the absorption of UV light to the collector electrode,
where  the current  (proportional to the  concentration)   is  mea-
sured.
Nondispersive Infrared Detector
     Nondispersive  infrared (NDIR) spectrometry is  a  technique
based  upon  the broadband  absorption characteristics  of certain
gases.   Infrared  radiation is  typically  directed  through  two
separate  absorption  cells:   a reference cell  and  a sample cell.
The  sealed  reference cell   is  filled with  nonabsorbing gas,  such
as nitrogen or argon.  The  sample cell is physically identical to
the  reference cell  and  receives  a continuous  stream  of the gas
being analyzed.   When a particular hydrocarbon is present, the IR
absorption is proportional  to the molecular concentration of that
gas.  The detector  consists of a double chamber separated by an
impermeable diaphragm.   Radiant  energy  passing through  the two
absorption cells  heats  the two  portions of the detector chamber
differentially.    The pressure  difference  causes   the  diaphragm
between the cells to distend and vary a capacitor.  The variation
                                8

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in capacitance  is  proportional to the concentration of  the  com-
ponent of gas present and is measured electronically.
     The NDIR  instruments  are  usually subject to  interference,
because other gases  (e.g.,  H20 and C02 )  absorb at the  wavelength
of the  gas  of interest.  Efforts  to  eliminate  the  interferences
by use  of  reference cells or optical  filters  are  only partially
successsful.  For  hydrocarbon (HC) monitoring,  the detector  is
filled with  one or several different  hydrocarbons, which  may  be
different from  the HC  contained  in  the sample;  this  causes  a
disproportionate response.   Other  sources of  errors include gas
leaks in detector  and reference cells, inaccurate  zero  and  span
gases, nonlinear response, and electronic drift.
Thermal Conductivity Detector
     The thermal conductivity of a gas provides a physical  method
of quantitative  measurement.7  The  method is  nonspecific,  how-
ever, for a mixture of gases.  When mixtures can be resolved into
components,  as in  a  chromatographic  column,  thermal conductivity
is used extensively.  For a mixture  of a few components in which
one gas with a high coefficient of thermal conductivity is  highly
concentrated, thermal  conductivity can  also be  used  with  some
success.   Often,  differential  measurement  can  eliminate  the
influence of  other gases,  so  that a  change  in concentration  of
the  gas  of  interest  can be  detected.  If a  combustible  hydro-
carbon is burned in  air,  the carbon dioxide concentration can be
measured before  and after  combustion, and  the change  in  carbon
dioxide is related  to the hydrocarbon content.  In applying this
technique,   one  must  consider  the increased  water vapor  as  a
product of  combustion.    It can be  accounted  for  by  drying  or
saturating  the  sampled air  stream before and  after  combustion.
Although the solubility of carbon dioxide in water is low,  such a
procedure  at very low  hydrocarbon  concentrations can present
additional problems.

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Hot Wire Detector
     The heat of combustion of  a  gas  is  sometimes  used for  quan-
titative detection of that gas.   Suffering the  same limitation as
thermal conductivity,  this method is nonspecific and depends upon
sampling and measurement conditions to give satisfactory results.
     One type of thermal combustion cell  uses a resistance bridge
in which  the  arms  of the bridge are  heated  filaments.   The com-
bustible gas  is  ignited in a  gas cell upon contact with a heated
filament,  and the  resulting  heat  release changes  the  filament
resistance, which  is  easily measured  and related to the gas con-
centration.
     Another combustion method uses catalytic heated filaments or
oxidation  catalysts.   Filament temperature  or  resistance change
is measured and related to gas concentration.

REFERENCES
  1.  U.S.  Environmental Protection Agency.  Measurement of Vola-
     tile  Organic  Compounds.  EPA-450/2-78-041,  1979.
  2   Salo,  A. E.,  S.  Witz, and R. D. MacPhee.  Determination of
     Solvent  Vapor Concentration by Total  Combustion Analysis:  A
     Comparison  of  Infrared  With  Flame  lonization   Detectors.
     Presented  at  the  68th Annual Meeting  of  the Air  Pollution
     Control  Association,  Boston,   Massachusetts,  June  15-20,
     1975.
  3.  Personal communication between Johnson,  L.  D.,  U.S. EPA,  and
     M. Y.  Anastas,  PEDCo Environmental,  Inc.   December   19/9.
  4.  Byron Instruments, Inc.   Air Quality Analytical Instruments.
     Promotional literature.   1979.
  5.  U.S. Environmental  Protection Agency.   Control  of Volatile
     Organic Emissions from Existing Stationary Sources.   Volume
      I:   Control   Methods   for   Surface  Coating  Operations.
      EPA-450/2-76-028, 1976.
  6  Willey  M   A.,  and C.  S.  McCameron,  Jr.    Evaluation  of
      Portable,   Direct-Reading   Hydrocarbon   Meters.    National
      Institute  for  Occupational  Safety and   Health.   HEW  No.
      (NIOSH) 76-166.
                                 10

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7.  American Conference  of Governmental  Industrial  Hygienists.
    Air  Sampling  Instruments  For  Evaluation  Of  Atmospheric
    Contaminants.  5th ed.   1978.
                               11

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                            SECTION 3
                    PORTABLE VOC INSTRUMENTS

     PEDCo conducted a survey to obtain information about perfor-
mance characteristics and costs  of portable VOC instruments,  and
several  instrument  manufacturers provided  literature  describing
their  instruments.   PEDCo  telephoned  the  manufacturers of  the
more promising  instruments  to  determine their current and future
development  activities  to reduce  costs  and develop new applica-
tions.  The results of the survey are summarized below.

PERFORMANCE CHARACTERISTICS
     Before  surveying  instrument  manufacturers,   PEDCo defined
instrument parameters  and performance specifications of interest
for  this  task.  Based on consultation with  in-house personnel who
are  familiar  with  the  operation and  capabilities  of various
monitoring instruments, PEDCo  compiled  Table  1,  a  list  of instru-
ment parameters that are necessary for  a complete description  of
the  instruments.   From this  list,  PEDCo developed a survey  form
to help summarize data  and  identify gaps in information.

 SURVEY OF INSTRUMENT MANUFACTURERS
      Tables  2,  3,  and 4 list the instrument  manufacturers  most
 likely to offer  portable ionization detectors,  infrared  instru-
 ments,  and  combustibles  analyzers.   Sources  of  information in-
 cluded:  "Analytical Chemistry,"  October 1978; "Thomas Register"
 for 1978; "Pollution  Equipment News,"  April  1979;  the exhibitor
 listing  for the 1979  Pittsburgh Conference on Analytical Chemis-
 try  and Applied  spectroscopy;  and  the  fifth  edition of  "Air
 Sampling Instruments for Evaluation of Atmospheric Contaminants,"
                                 12

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                        TABLE 1.   INSTRUMENT  PARAMETERS
Class - Portable:   Instrument can be readily transported for field  use.

Principle of Operation - The technique used to detect and measure the  pollu-
     tant or parameter.

Lower Detectable Limit - The smallest quantity or concentration of  a sample
     that causes a response equal to twice the noise level.   (Not to be  con-
     fused with sensitivity, which is response per unit of concentration.)

Range - The lower and upper detectable limits.   (The lower limit is usually
     reported as 0.0 ppm.  This is somewhat misleading and should be reported
     as the true lower detectable limit.)

Interferences - Any substance or species causing a deviation of instrument
     output from the value that would result from the presence of only the
     pollutant of concern.

Multiparameter Capability - Ability to measure other pollutants or  parameters.

Sampling Method - Specified as continuous, semicontinuous, or intermittent.

Accuracy - The difference between the measured value and the true values which
     has been established by an accepted reference method procedure.  In most
     cases, a value is quoted by the manufacturer, and no description is given
     to indicate how this value was obtained.

Precision - The degree of variation between repeated measurements  of the same
     concentration.

Noise - Spontaneous deviation from a mean output not caused by input concen-
     tration changes (expressed as a percentage of the full scale).

Lag Time - The time interval from a step change in the input concentration at
     the instrument inlet to the first corresponding change in the   instrument
     output.

Rise Time - The time interval between the initial response and a 90% response
     (unless otherwise specified) after a step increase in the inlet concen-
     tration.

Response Time - The time  interval from a step change in the input concentra-
     tion at the instrument  inlet to a reading of 90%  (unless otherwise speci-
     fied) of the  ultimate recorded output.  This measurement is the same as
     the sum of lag time  and rise time.

(continued)
                                       13

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TABLE 1.   (continued)

Fall Time - The time interval  between  the  initial  response  and  a  90% response
      unless otherwise specified)  after  a  step  decrease  in  the  inlet concen-
     trTlion.   This measurement is usually,  but not  necessarily,  the same as
     the rise time.

7pro Drift - The change with time  in instrument output over a stated time
?er° geHod of unadjusted continuous operation  when  the input concentrate  is
      e
     zero (expressed as  a  percentage  of  the  full  scale).

     Drift - The change  with time in  instrument  output  over  a  stated  time
     °p r od ofunaSjusted  continuous  operation when the input  concentration  is
     "stated value other  than zero (expressed as a percentage of the full
     scale).

An.hi.nt Temperature Range  - The range of ambient temperature over which the
- instrument meets stated performance specifications.

Calibration - The method for determining thelnstruiient response to calibra-
- tTbTgases (dynamic calibration) or artificial stimuli  (static calibra
     tion).

Warmup Time - The elapsed time necessary after startup for the instrument to
     meet  stated performance specifications when the instrument has been shut
     down  for at least 24 hours.
                                        14

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                                             TABLE 2.  PORTABLE IONIZATION DETECTORS
   U1



Manuf ac turer
Analytical
Instrument
Development.
Inc .
Avondale,
Pennsylvania









8endi». Envi-
ronmental and
Process Instru-
ments Division,
Levisburg.
West Virginia
Century
Systems.
Arkansas City,
Kansas


General Elec-
tric. Instru-
ment Products.
iv nn
Massachusetts
*eati Consul-
ta-«ts. Inc .
>l?uqhto".
Massarnuset t«.

Model
No
550b
and
551

555C



5H-l2d





8401*




OVA- 118
OVA- 128f
OVA- 98
OVA- 1089

TVM-1



Detecto,
PftK II




Pollu-
tant(s)
detected
Nonmethane
total hy-
drocarbons

Total hy-
drocarbons



Total hy-
drocarbons
and i nd i -
vidual
compounds
with GC
| Total hy-
drocarbons

i

! Total hy-
drocarbons
1 Total hy-
drocarbons
Total hy-
1 drocarbons
Total hy
! drocarbons
Halogenated
compounds
i


Total hy-
drocarbons

i


Principle
of "e
operation Cost, S
FID J 3711 1

FID 3987 2
1


,
FIO/CC 4968
1

I !


FID \ 3195
i

1

FID 3500
FIO/GC 4200
FID 3500
FIO/GC 4200

Ion h 4060
capture



F|D ?950 !

i


ight, : Range,
Ib ppm
6 5 0-200 and
0-2000 for
Model 550,
0-200 and
0-10,000, for
Model 551
0 5 0-10,000,
0-2000. and
i 0-100


Accu-
racy,
13


Sensi-
tivity
0 1 ppm
on a
scale
of
• 0-200
13
1 1

(
41 '.
i






40 1-1000 1 12




12 0-10 and
0-100
i2 0-1000



12
12
12 0-10.000 12
ppm
1 ppm on
a scale
of
0- 2000
ppm

0 05 ppm
as pro-

pane



0 01 ppm




0 2 ppm
methane
0 2 ppm
•ethane
0 5 ppm
Ml han»
12 0-10.000 12 05 pp("
i methane

23 9 ranges *10 01 ppm
0- 1 through ,
0-10,000

! '

8 0-10 J 2 ppi»
0-100 14 2 ppm
0-1000 , J ; 5 PP"



Pre-
cision,
t
13


Re-
sponse
time, s
S


Noise
Less than
0 1 pp"
on a
0-200
PP"
13


5


1 ppm
on a
scale
of
0-2000
1 ppm

i




i
1







tem-
pera-
ture.
°C
0-40

0-40



Drift*






5-45 !
j




i • •
12 ' 8 !t«

j



12
2 1
5-40





i = lit <2«)
s = lit (24)
i
i
i
1

-20 to s = lit (1)
40 !
-20 to s = Ht (1)
• 40
tt ' 2 -20 to , s = in <>)
1 40
1 -20 to s = lit (1)
! 40
1 ' .1
120 . 0-55
• Negl igible
i
• i
1


1 'S ^ ,...»,„
S-^,7,
1

(continued)

-------
             TABLE 2.  (continued)
Manufacturer
HNU Systeai.
Inc .
Newton
Upper Falls.
Massachusetts








Melroy Labs
Springfield,
Virginia

Mine Safety
Appliances
Co .
Pittsburgh.
Pennsylvania
Survey and
Analysis.
Inc
No'thboro,
Massachusetts




Model
No
Pl-1011









HC-500

Total HC
analy-
zer


Snlfty
Model
A-500





Pollu-
tant(t)
detected
Chlorinated
hydrocar-
bons, aro-
matic*.
aldehydes.
ketones ,
any sub-
stance
which ad-
sorption
of UV
light
results In
ionfzatlon
Total hy-
drocarbons

Total hy-
drocarbons



Total hy-
drocarbons





1 1
Principle ,
of (Weight. Rang*.
operation Cost, f Ib ppai
Photolon- ' 3395 <9 ; 0-20.
Izatlon , i 0-200. and
0-2000


i
,




i
FIO ' 40 0-10.
0-50,
0-100.
0-500. and
0-1000
FIO 3850 35 0-4 and
1 0-12.000
!


FID 1695 17 0-10
for
basic 0-100
unit,
SJ295 0-1000
entire 0-10.000
po-ta-
C'lity
package
Accu-
racy.
lj









tl on
low
scale

til



-55
-35
-3
•20
I


Sensi-
tivity
1 pp*









0 1 PP»
CH4





2 PP"


i



Pre-
clilon.
1










tl












tponse
tlM. S
5
i







I
' 45
1

1 1



4






Noise









i
•tO 05
PP»
CM.
|
to sx
1



i






tablent
leer
pera-
ture,
•c
-IB to
SO






1


10-40
i
*t
i 4-45
i


0-50






Drift*
I - « (7)
f - 31 (6)
for a range
O f 0' a?0 DOB *
no drift for
other ranges








z = 0 2 pp. (24)
s = 0 2 PP" (24)
for a range of
0-10 PP"

s = 0 51 (24)


1
= 1201 (7)
' = 1121 (7)
= 0
= 141 (7)
= 10 n (7)
. = 0
= to n (7)
= 0



(continued)

-------
TABLE  2.    (continued)
   * The letters "i" and "s" Indicate lero  drift and span drift   The numbers of hours  over which drift occurs Is given In parenthesis
   b A charcoal tub* Is used to adsorb organic! except -ethane, and a range of 0-10 ppm Is available with the recorder   The Instrument can be used as alar
     by setting In 0-1000 range   This is a screening and leak detection device
   c The following features are available    a  range of 0-100 ppn with recorder only. Internal power, oxygen, and hydrogen supplies,  a heated probe; and a
     battery-operated recorder with a range of 0-100mV d c
   ** Capabilities equal or exceed those of  Models bbO and 555
   ' Capabilities to detect higher concentrations require further Investigation   This  My be suitable for anbient air measurement only

     Optional GC
   9 Optional CC
   h A heated platinum wire embedded In rubidium combusts incoming gases   Combustion of halogenated materials causes electrons to flow from the rubidium
     The electrical flow Measured is proportional to the amount of halogenated materials present
   1 Performance characteristics as measured by H10SH   Reference 6, Section 3
   •* Inaccurate

-------
                                              TABLE 3.   PORTABLE INFRARED INSTRUMENTS
Manufacturer
Anarad, Inc .
Santa Barbara,
California













Aitro
Resources
Corp .
Houston.
Texas
Chrysler
HuntivHle
Electronics
Division
Huntiville,
Alabama
Foxboro
Analytlctl.
Wilks Infra-
red Center.
S Norvalk.
Connecticut










Nodal
No
AR-400b















5000e




in-cd

Nopar"
,f
Atlas"
Pol lit- Prlnc
tant(s) of
detected opera
Individual IR
ipecies
absorbing •
IR :
1
,
•
I
•



I


I
Iple
tlon Cost. $
2195
for an
analy-
icr aea-
surlng
1 single
gas
5745
weight,
Ib








for an
analy- i
1 ler Mea-
suring
three >
• gases
. (Node!
403)
Individual IR ' 25
hydro-
carbons


' 1
.
,

Total hy- IR 20
drocarbons
Range
















Specified
by custom-
er , up to
100X

0-300 and
0-2000 DM
Total hy- IR 20
drocarbons

Total hy- IR 30
! drocarbons
1
Hlran Any species IR
-104* absorbing IR
between 2 5
and M 5 urn






Hlran-lA





In wave-
length




Any species IR
absorbing IR
between 2 5
and 14 5 pn
in wave-
length

0-300 and
0-2000 pp»
0-300 and
0-2000 pp»
Not sold 24 ppte to per-
in cent
United '
Stales
but
. price '
•ay be ,
sfmi lar
to
Accu-
racy.
X
11















il




a

a

12

15








Miran-lA i
6600 32
-2
1




Re-
sponse
tiae. i
5




















6
Noise, X








Aa*l«nt
tem-
pera-
ture,
•c
0-49


1




i
i
Drift1
I * 11X (24)
a = IIS (24)








• i

















-40 to
55








z = 
46

I.'.IO. ' C-46 l = 10 3* (8)
jrfl
«.. ,






1 •



1.4 10. 0 3 0-40 1 = 10 Z* (8)
«-: 40



1
    CD
(continued)

-------
                      TABLE  3.    (continued)
VO
Manufacturer
Gas Tech. Inc ,
Mountain View,
California




Infrared
Industries.
Inc ,
Santa
Barbara,
California











Mine Safety
Appliances Co. .
Pittsburgh,
Pennsylvania
Node!
No
Halide
de-
tector



Pollu-
tant(s)
detected
Halogenaled
hydrocar-





IR-711 Alkane hy-
drocarbons


l
lR-702f Any species


absorbing
IR
IH-703 Any species

f
!R-705r
absorbing
IR
Any species
absorbing
1 IK



LIRA
303s




Hydrocarbon
species
that
absorb 1R
Principle
of
operation
Enhance-
ment of
radia-
tion
from a
spark by
halogens
IR (solid
state
detect-
or)

IR


IR
Cost, S
1125






1250




2895


2395
Weight,
Ib
13






9




34


34
i i

IR





IR
•
2950


34


'




2970 i 37
1






Range
0-100 and
0-10,000
PP«




0-100* LEI
and
0-1000 pom
IR 702.
1R 703, and
IR 70S are
available
•tth analog
or digital
scales.
analog scales
range from
0-1 00* to 0-
200 ppm,
digital
scales range
fro- 0-lOOZ
to 0 IX
0-100* IEL
and
0-1000 ppm

Accu-
racy,







t5




tl















Sensi-
tivity




Pre-
cision,
I




j





Re-
sponse
tlM. S
5






15 120


i
'
I






t
'
'
i
i
i


Noise. 1










I

«

1
»





i
•
i
i



,
11 5 <1


1
1



tabUnt
te»-
pera-
ture,
•c







0-50




0-50











4-45

Drift*







I = Itt (8)




z = tit (24)
s = tlX (24)










I = 
-------
                                             TABLE 4.  PORTABLE  COMBUSTIBLES  ANALZERS
  10
  o
Manufacturer
lacnarich
Instrument Co. ,
Santa Clara.
California


Blomarlne
Industries.
'1C ,
Malvern,
Pennsylvania


Control
Instruments
Corp ,
Fairfleld.
New Jersey
Gas Tech. Inc ,
Mountain View,
California



International
Sensor Tech-
nology.
Santa »ru.
Cal ifornia

Mine Safely
Appl lances
Company ,
Pittsburgh,
Pennsylvania




Model
No
G
l_
H°
Tl»
Sniffer'

922


900.
900*.
and
900RS
FF*Pd




1J77


1238


AGS100





20e

f
30f


40"


Pollu-
Unt(s)
detected
Combustible
gases




Combustible
gises and
vapors
Combustible
gases and
vapors

Flammable
gases and
vapors


Combustible
gases

' Combustible
l gases
i
Combustible
gases and
vapors



Combustible
gases

Combustible
i gases

Combustible
gases

Principle
of
operation
Catalytic
combus-
tion
Catalytic
combus-
tion
Catalytic
combus-
tion
Catalytic
combus-
tion

Thermal
combus-
tion


Catalytic
combus-
tion
Catalytic
combus-
tion
Change in
resist-
ance
•tthin
detector

Catalytic
' combus-
tion
Catalytic
combus-
tion
Catalytic
combus-
tion
Cott. S
2S3
160
279
896


49S


68S
695. and
7IS






S2S


69S


1200
for ppm
1 scale.
B2S (or
LEL
scale
374


! 374
i

' 374
i

Weight.
Ib
4
4
S
5


1.5


3



28




6


7








6








Range
0-100* LEL
0-10CX LEL
0-100* LEL
0-100.
0-1000. and
0-10.000 ppm
0-100* LEL


0-100* LEL



0-100* LEL




0-1 DOS LEL


0-100* LEL
and
0-SOO ppm
LEL and ppm




1
0-100* LEL


, 0-IOOX LEI


0-10* and
0-100* LEL

Accu-
racy,
X



13


tSX LEI


15* LEI



13




ts


M


tS














Sensi-
tivity



t ppm



































Prt-
clilon,
X



±3









11




±2


12


t5














tponsa
time, i






S


S



<10




4


10


ID on
LEL
scale
and 60
on ppm
scale









mjfttwil
tar
pera-
tur«.
•c
o-so





-IS to
40

-IS to
40


0-52




0-40


-20 to
SO
















Drift'













1 = <1« (1 yr)
S = <15X (1 yr)









Negligible In
a 3-month
period

i
i









(continued)

-------
TABLE  4.    (continued)
Manufacturer
Survey and
Analysis, Inc
Northboro.
Massachusetts
Teledyne
Analytical
Instruments.
Jan Gabriel,
Call forma
Model
Mo
OrMark
I*"'
980
•ollu-
Unt(s)
detected
Combustible
gasef and
vapors
Total com-
bustibles
and oxygen
Principle
of
operation
Thermal
conduc-
tivity
Catalytic
combustion
Cost, t
28S
Weight.
Ib

-------
published by  the  American Conference  of  Governmental  Industrial
Hygienists in 1978.
     Instrument manufacturers were requested  to  provide informa-
tion on  portable  instruments that are capable of  detecting  and
measuring VOC  concentrations from 10  to  10,000 ppm.   PEDCo  de-
cided that  instruments weighing 40 Ib or  less may  be  considered
portable.   Although most  manufacturers  were responsive  to  the
survey,  information received after the initial contact was usual-
ly  incomplete.   Followup  contacts  were  often  necessary.   After
the list  of  manufacturers  was exhausted and the accumulated data
were analyzed, manufacturers of apparently promising instruments
were again contacted  to determine their plans for further devel-
opment.    Specifically,  they  were asked to project future costs on
the  basis of  order of magnitude  increases  in  demand  for their
instruments.

SURVEY RESULTS
     Four classes  of  detectors  or  methods of VOC  detection and
measurement) were  revealed by the survey.  These are:
     lonization detectors
     Infrared detectors
     Combustibles  analyzers
     Miscellaneous instruments,  including detector  tubes  and
     intermittent  colorimetric  methods
Data  on  performance  characteristics,  measurement  capabilities,
and costs are  summarized below.
 lonization Detectors
     The performance characteristics  of  ionization  detectors  are
 summarized  in  Table 2.   Prominent  among  these  are  the  FID's,
 which  can measure TGNMO or  individual organic compounds.   When a
 GC option  is available,  the instrument  can be used  to  measure
 concentrations of various  components  in a mixture, after  cali-
 bration curves are obtained for each component.

                                 22

-------
     In general,  instruments with FID detectors,  are  read  direct-
ly and  are more  accurate  in  the range  from 0  to  10 ppm  than
infrared instruments.  They do not  respond  to water vapor,  but
particulate matter must be removed from the gas sample.
     PEDCo  found  only  one photoionization  detector  (the  HNU
Systems  Model PI-101)  that uses  ultraviolet  light  to  effect
ionization.  As  with FID's, the  detector's  response varies with
the  functional group in  the organic species.  Although  the in-
strument has  been used as  a screening  device for leak detection
in processes  involving synthetic organic chemicals,  its applica-
bility in compliance determinations,  especially when mixtures are
involved,  is  uncertain.   The unit is not known to have been used
for  measuring organic  species  that had been  separated with a GC.
     Another  ionization  instrument detector  is the General Elec-
tric Model TVM-1  for measurement of halogenated species.  Litera-
ture  about the instrument  suggests  that combustion  of the halo-
genated  organic  species  results in  an  electronic  flow  whose
magnitude  is proportional   to  concentration.   The  manufacturer
recommends  using  the instrument in  industrial  hygiene appli-
cations.   Its use,  however, in  determining VOC  emissions  from
such sources  as degreasers  and  drycleaning systems  should be
explored,  because  the  detection  range suggests  suitability to
these sources.
     The costs of available ionization  detectors  range from  $2300
to  $5000.   Addition of a GC unit  can increase the cost by  $1000.
The  lowest priced  FID has been  used to detect methane  in  leaks
from pipelines and  in sewer gases.   The FID's used as screening
devices  for  leak detection  in  the  petroleum  and  petrochemical
industries (such as the Century Systems and HNU  Systems instru-
ments) cost about $3500.
Infrared Instruments
      Performance characteristics  of portable infrared detection
devices  are  summarized  in  Table  3.   These  devices  are  suitable
for the  detection  and  measurement  of single organic  compounds.
                                 23

-------
The  wavelength  at  which  a  certain compound  absorbs  infrared
radiation is predetermined, and  the  device  is preset (by the use
of optical  filters)  for that  specific  wavelength.   If  set  to  a
wavelength of  3.4  micrometers, infrared  devices  can be  used  to
detect  and  measure petroleum  fractions,  including  gasoline and
naphtha, which  are  known to be mixtures  of aliphatic  (saturated
and unsaturated) and aromatic hydrocarbons.
     Particulates and water vapor  should  be removed from VOC gas
samples  to- be  measured.  Water  absorbs IR radiation  over the
entire  spectrum.   The IR devices can be  used to  determine TGNMO
in mixtures by  setting  the device to one component  if the rela-
tive concentrations of the constitutents do not vary or by chang-
ing the  setting  of  the  wavelength to accommodate each component.
     The costs of available IR detection devices range from $1250
to $6600.   The less expensive instruments  (such  as  the  Infrared
Industries  Model IR-711)  do  not  offer built-in multiparameter
capabilities  and require  calibration  at the  factory.   The more
expensive  devices  (such  as  the  Foxboro-Wilks  Model  Miran-lA)
offer  multiparameter  capabilities and  can  measure  a wider range
of concentrations.
Combustibles Analyzers
     Performance characteristics and capabilities of combustibles
analyzers are  summarized in  Table 4.  With  few exceptions,  these
instruments measure VOC concentration as a  percentage of the LEL
of combustible hydrocarbons; the LEL is generally on the  order  of
10,000  ppm.
     Currently,  these  analyzers  are used  in leak  detection and
explosion-safety applications.   The detectors  are nonspecific,
and  with the  exception of  the  Bacharach  Model  TLV Sniffer and
International  Sensor  Technology Model  AG5100,  their  accuracy  in
the  range from  0 to 100 ppm is questionable.
     The costs  of these  instruments  vary  from $160 to  $1200.
More expensive units  can measure  concentrations  in  ranges from 0
to 1000 ppm and 0  to  100 ppm.
                                 24

-------
Miscellaneous Instruments
     PEDCo found other instruments  that  may be useful in compli-
ance determination for various  sources of VOC.  For example,  Gas
Tech, Inc., of Mountain View, California, offers two commercially
available devices for detection of halogenated hydrocarbons.   The
first,  called  Halide Detector,  operates  on  the  principle  of
enhancement of  UV  radiation  emitted from a spark in the presence
of  halogenated  species.   This  instrument weighs  13  lb,  costs
$1125,  and has  concentration  ranges of 0 to  100  ppm  and  0 to
10,000 ppm.  Another  instrument offered  by the same manufacturer
acts  as  an  alarm  for  the  presence of halogenated  species at
preset  concentration  levels in the range  of  0 to 100  ppm;  the
alarm costs $400.
     A number  of potentially useful methods can measure individ-
ual  organic  species  at  concentrations below  or at  the threshold
limit value  (TLV)  and up to several  thousand parts per million,
depending on species.  These methods involve passing a gas sample
of known volume through  a small glass detector tube.  The tube is
packed  with  a sorbent that has been  impregnated with a chemical
reagent known to produce a coloration or stain in the presence of
the  organic  species  of interest.   The length of stain or colora-
tion produced indicates  the concentration,  and calibration charts
that relate stain length to concentration are provided.
     Detector   tubes  certified  by  the   National   Institute  for
Occupational  Safety  and Health are sold in packages  of 10 tubes
at  a cost between $13 and $30  per  package, depending on species
to  be measured.   The pumps used to  meter known volumes  of gas
through  the  tube usually cost  about  $200.   Two manufacturers of
detector  tubes  and pumps are Mine Safety Appliances and National
Draeger,  Inc.;  both firms are in Pittsburgh, Pennsylvania.
     The  accuracy  of  detector  tubes is  about ±25 percent at  five
times TLV and ±35  percent at one-half TLV.  The precision ranges
from  10 to 15  percent,  but is  difficult to quantify because of
                                25

-------
variations among different batches of detector tubes.   The poten-
tial use  of detector tubes to determine VOC  compliance  would  be
restricted  to  situations  where regulations limit  the  concentra-
tion  of  a  given  species  (e.g.,  perchloroethylene  drycleaning,
where a limit of 100 ppm is specified).
Safety Certification
     Portable instruments to detect VOC emissions from stationary
sources  may be  used  in  hazardous  locations such as  petroleum
refineries  and bulk  gasoline  terminals.   The  National Electrical
Code requires that  instruments  to be used in hazardous locations
be  certified  to  be  explosion  proof,  intrinsically  safe,  or
purged.
     Hazardous   locations   are   divided   into  three   classes:
Class I,  Class II,  and Class III.   Each class  has two divisions
(Division 1  or  2)  according to the  probability that  a hazardous
atmosphere  will  be  present;  and also into seven groups depending
on  the  type of  hazardous  material  exposure.   Groups  A through D
are  flammable  gases or vapors,  and Groups E,  F,  and  G apply to
combustible  or conducting  dusts.   Class I,  Division 1,  Groups A,
B, C, and D  locations are those in which hazardous concentrations
of  flammable gases  or vapors  may exist under normal operating
conditions.  Class I, Division 2, Groups A, B,  C,  and D locations
are  those  in  which hazardous  concentrations  of  flammables may
exist only  under unlikely conditions of operation.
     Only   five  manufacturers  produce  certified portable  VOC
detection  instruments.  Table 5  lists  these  manufacturers, ap-
proved  instrument  model  numbers,  and  instrument certification
categories.
                                 26

-------
                                     TABLE  5.  PORTABLE VOC DETECTION  INSTRUMENT CERTIFICATION
K)
              Manufacturer
       Bacharach Instrument Co.,
        Santa Clara, California
Century Systems,
 Arkansas City,  Kansas

HNU Systems, Inc.
 Newton Upper Falls,
 Massachusetts

Mine Safety Appliances  Co.,
 Pittsburgh, Pennsylvania

Survey and Analysis,  Inc.,
 Northboro, Massachusetts
                             Model No.
                            TLV  Sniffer
                                      OVA-128
                                      OVA-108

                                       PI-101
                                     OnMark
                                     Model 5
                                                                        Certification
Intrinsically safe,  Class I,  Division 1,  Groups C & D
Intrinsically safe,  Class I,  Division 1,  Groups C & D,  and
 Class I,  Division 2, Groups  A & B

Intrinsically safe,  Class I,  Division 1,  Groups A, B, C, & D
Intrinsically safe,  Class I,  Division 1,  Groups A, B. C, & D

Intrinsically safe.  Class I,  Division 2,  Groups A, B, C, & D
Intrinsically safe. Class I, Division 1, Group D, and
 Class I, Division 2, Groups A, B, & C

Intrinsically safe, Class I, Division 1, Groups A, B, C, & D

-------
                            SECTION 4
                 CONCLUSIONS AND RECOMMENDATION

     Of the  four classes  of VOC detectors described in  the  last
section,  ionization  detectors  appear  (1) the most versatile  in
terms of applicability  to various  sources  of VOC, (2)  the  most
accurate,  especially in the lower ranges (0 to 10 ppm)  of concen-
tration,  and (3) the most  sensitive,  both  in terms  of minimum
detectable  limit  and  instrument   response  per  unit  change  of
concentration  in  the  lower  concentration  range.  This section
examines the applicability  of each instrument  class in  VOC  com-
pliance monitoring.

IONIZATION DETECTORS
     Ionization  detectors,   notably  FID's,  are  applicable  to
nearly  all  sources  of VOC.   Although  most current  models are
mainly used  to  detect hydrocarbon leaks in petroleum refineries,
petrochemical plants,  etc.,  they  can be modified to  measure VOC
control device  efficiencies,  source emission concentrations, and
fugitive emissions.
     As a  result  of  their  capability to  detect organic carbon,
ionization detectors may be used to determine mixtures as well as
individual  components.   If  the individual  species in a mixture
are  known,  the  components  can be  separated in a GC column, and
the  detector can be calibrated  for those species.
     For  a single component  a  GC  is  usually not necessary.  VOC
sources with a  single component include  perc  drycleaning systems
and  degreasers.
     Available  ionization  detectors can require  modifications to
improve  their  capabilities  for extractive  sampling from stacks,

                                 28

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vents, and ducts.  These modifications1may include provisions  for
removal of particulates and heating of sampling probe and line to
prevent loss of the sample through condensation.
      lonization  detectors  are  not  suitable   to  determine  the
compliance  of  sources  with  a  control  device  (such as  a  fume
incinerator)  that chemically  alters  emission  species.   In such
cases,  Reference  Method 25  should be  used to  measure organic
carbon.

INFRARED DETECTORS
      As  mentioned earlier,  infrared detectors  are  suitable  for
application when  only  a  single  component is  present  or  when
emissions  consist of  petroleum  fractions  (such  as  naphtha  and
gasoline)  in  the vapor phase.   The  less  expensive devices  are
calibrated for one  component at the  factory  or can use  optical
 filters  to change the  wavelength.   The more expensive devices can
 continuously vary wavelength  over the useful  infrared  spectrum.
      Where infrared  devices are used in extractive sampling of
 stacks and vents, provisions should be  made  for the removal of
 particulates and moisture.   The latter absorbs radiation over the
 entire spectrum.
      Infrared  devices  can  be  used  to  determine  compliance of
 surface coating  operations  if  a single-component coating is used
 or  if  the  devices  offer  multiparameter  capabilities  and  all
 coating components are known.  These instruments can also be used
 to monitor bulk gasoline plants, petroleum liquids storage facil-
 ities,  tank truck  gasoline terminals,   perc  drycleaning plants,
 solvent  metal  cleaning  operations,  pharmaceutical plants,  and
 pneumatic  tire manufacturers.
      The minimum detectable  limit  of many  infrared devices ranges
 from a  few parts per million to  100 ppm, depending  on species and
 path length  of the detectors.
                                  29

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COMBUSTIBLES ANALYZERS
     Combustibles analyzers  are  mostly used to  detect  leaks  and
monitor LEL percentages.  Potential uses in leak detection are in
refineries  and  facilities  for  petroleum  liquids  storage  and
loading.  Applications  involving the  measurement of LEL percent-
ages include surface coating operations, graphic arts,  and refin-
eries.
     In surface coating operations  that operate spray booths and
bake ovens  in  the  range of 10 to 25 percent LEL, the accuracy of
these devices  can  be sufficient  for  control and  maintenance of
this level  of combustibles.  In their  present  state of develop-
ment, however, combustibles analyzers cannot be used to determine
compliance because they offer no  reliable methods of data inter-
pretation in terms of organic carbon and because (with the excep-
tion of the Bacharach Model TLV Sniffer) their accuracy in ranges
from 0 to 100 ppm and 0 to 1000 ppm is in doubt.

MISCELLANEOUS INSTRUMENTS
     Detector  tubes  with  proven  accuracy  and  precision  can be
used to  determine compliance  if the organic species  is known.
Their applicability may be limited  by the recommended concentra-
tion range in which they can be used.

DEVELOPMENT PLANS
     After  completing  the initial  survey,  PEDCo contacted a se-
lected number  of instrument manufacturers  to  obtain information
on  their  plans for  further development.   Specifically,  PEDCo
asked the following questions:
     Are there  plans  for further  development of currently avail-
     able models  in  order  to reduce  cost  and  improve  capabili-
     ties?
     What  reductions  in costs  (if any) can  be  anticipated if
     demand increases tenfold?
                                30

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     what  are  the  current  and  projected  applications  of the
     available  instruments  in theF  monitoring  of emissions  from
     sources of VOC?
     in  general,   instrument  manufacturers were  reluctant  to
develop  further  capabilities  and  applications of  their  instru-
ments before a clearly positive demand develops.  One manufactur-
er  currently plans  to  develop another  portable photoionization
(ultraviolet)  detector,  and  another  is developing  temperature
controls for the GC column in a GC/FID instrument.
     Approximately   one-third  of  the  manufacturers  contacted
mentioned  that a  fivefold to  tenfold  increase  in demand would
reduce  the costs  of their instruments by 10 to  15 percent.  Many
said they  would not  reduce costs  for  such increases in demand,
and others could not provide  answers.
                                  31

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   APPENDIX



SOURCES OF VOC

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                         SOURCES OF VOC

SOURCES AND EMISSIONS - GENERAL
     As of  November 1979,  CTG documents covering the  following
industries and activities had been issued:1'21
     1.   Surface coating  of cans, coils, paper,  fabrics,  auto-
          mobiles,  and light-duty trucks
     2.   Surface coating of metal furniture
     3.   Surface coating of insulation of magnet wire
     4.   Surface coating of large appliances
     5.   Surface coating  of miscellaneous metal  parts  and pro-
          ducts
     6.   Factory surface coating of flat wood paneling
     7.   Graphic arts—rotogravure and flexography
     8.   Bulk gasoline plants
     9.   Storage of petroleum liquids in fixed roof tanks
    10.   Tank truck gasoline loading terminals
    11.   Refinery  vacuum  producing systems,  wastewater separa-
          tors, and process unit turnarounds
    12.   Use of cutback asphalt
    13.   Gasoline service stations
    14.   Leaks from petroleum refinery equipment
    15.   Manufacture of vegetable oils
    16.   Petroleum  liquid  storage  in external  floating  roof
          tanks
                               A-l

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    17.    Perchloroethylene drycleaning systems
    18.    Gasoline tank trucks and vapor collection  systems
    19.    Solvent metal cleaning
    20.    Manufacture  of   synthesized  pharmaceutical   products
    21.    Manufacture of pneumatic rubber tires
     The  first  six  industries  are coating  operations  in  which
surfaces are cleaned and dried before single or  multiple coatings
are applied.  Coatings can be applied by dipping,  flowcoating,  or
electrostatic spraying.  After each coating is applied,  the parts
may go  through  a  flash  tunnel  to allow the  coating  to flow out
properly  and  through a bake  oven to  cure the  coating.   The ap-
plied coatings are usually polymers,  such as polyesters  and epoxy
resins,   and their  application  requires the  use of  solvents  as
thinners to reduce viscosity.  The solvents used can consist of a
single component or a mixture of aliphatic and aromatic  hydrocar-
bons, ketones,  esters,  and  alcohols.   Many of the  solvent mix-
tures form  explosive  mixtures with air upon evaporation from the
coated parts  in  such process equipment as spray booths, flashoff
tunnels,  and bake ovens.   Fire  insurance  underwriters  require
that  the concentration  of combustibles be  maintained  below  25
percent  LEL unless adequate LEL monitoring equipment is used (in
which case  50 percent LEL is  allowed).
     Many  spray  booths,  bake  ovens,  etc.  are operated  in the
range from  5  to 15 percent LEL to prevent leakage of vapors into
the  work area.   Also,  in spray booths  where worker exposure is
likely,   the LEL is maintained at or below 1  percent.  As a rule-
of-thumb, 100 percent LEL results from the evaporation of 1 gal-
lon  of  solvent in  2500  standard  cubic feet of  air.22  Depending
on molecular  weight and density,  this may result in  a  concentra-
tion of  about 10,000  parts  per million by volume (ppmv).
     Emission  reduction alternatives  for  surface  coating opera-
tions  include  (1) the  substitution  of powder,  water borne,  or
high-solids coatings, (2) the use of  activated carbon  adsorption
                                A-2

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to control  emissions from  application and  flashoff areas  when
conventional solvents are used,  and (3) the use of fume  incinera-
tion for reduction of emissions from bake ovens.  A typical regu-
lation  limits  emissions  to 0.36  kilograms  VOC/liter  (3.0 Ib
VOC/gal) of coating applied.
     When control  devices such as  activated carbon adsorbers or
fume incinerators are used, the regulations may specify the effi-
ciency  (80 to 95 percent) at which the device should be operated.
     Hydrocarbon emissions  from bulk gasoline plants result  from
filling of  trucks and  storage  tanks  and  breathing and drainage
losses  from  storage  tanks.    Control  alternatives  include the
utilization   of  submerged  filling  and  vapor balance systems.
Compliance  monitoring  would  consist of  onsite  inspections  to
ensure  that proper operating procedures  are  implemented.
     Hydrocarbon  emissions  from  fixed-roof  tanks  may  be  con-
trolled by  installing internal  floating  roofs.
     Hydrocarbon  emissions from tank  truck  gasoline loading ter-
minals  result from filling of  tank trucks  and from leaks  in pumps
 and pipe fittings.   Vapor recovery or combustion  devices  can  be
 used to control emissions from filling operations.
      Control  of emissions from refinery vacuum producing  systems,
 wastewater  separators,  and  process  unit  turnarounds   usually
 involves  modifying  the  operating  procedures  or  changing  the
 process  so  that hydrocarbon  emissions  from the various  sources
 are manifolded to the refinery flare system.
      The VOC emissions  from  the  use of cutback  asphalt  can  be
 controlled by  substitution of emulsified asphalt involving only
 water  and an organic emulsifier.
      Emissions  of  halogenated hydrocarbons  from  solvent  metal
 cleaning operations can be controlled  by implementing operating
 procedures that minimize solvent loss and by retrofitting  control
 systems, such as carbon  adsorbers  and freeboard  chillers.
      In  September  1979,  the  EPA  issued a  guidance document  to
 state  and local agencies that  contained model  regulations  affect-
 ing nine industries and  activities.23   Table A-l summarizes
                                 A-3

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                                      TABLE A-l.   CONTROL  OF  VOC  EMISSIONS FROM STATIONARY SOURCES
Industry 	
Petroleum
refinery
equipment

Surface coat-
ing of mis-
eel laneous
metal parts




Surface coat-
ing of flat-
wood panel ing
Source
Leaks from pipe
connections,
valves, pump
seals, etc.
Same as above
Spray coating,
flow coating
(flashoff)


Ovens

Coating operations
Pollutant species
Hydrocarbons
Hydrocarbons
Ketones, esters,
alcohols, ali-
phatic HC,
ethers, aromatic
HC, terpenes
Same as above
Same as above
Same as above
Same as above
Ketones, esters,
alcohols, hydro-
carbons, toluene,
xylene
Uncontrolled
concentration,
ppm
>10,000
>10,000
100-4003
100-4003
100-4003
100-800a
100-8003
100-300b
Controlled
concentration
Negligible
Negligible
10-100 ppm
(60 to 90%
reduction)
5-40 ppm
(90% reduc-
tion)
90% reduction
90% reduction
90% reduction
2.9-5.8 kg
per 100 m2
Control
method
Repair leak im-
mediately
Repair leaks dur-
ing shut down
Waterborne coating
Carbon adsorption
Incineration
Carbon adsorption
Incineration
Afterburner carbon
adsorption
Stream
pressure


Slightly
below at-
mospheric




Slightly
below at-
mospheric
temper
ature
Ambien
Ambier
Ambien
Ambien
Ambie-
ioo°-
400°F
ioo°-
400° '
Amb i e i
V
I
    (continued)

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   TABLE  A-l.   (continued)
i
Lfl


Industry
Synthesized
pharmaceuti-
cal products
manufacture
Pneumatic
rubber tire
manufacture








Graphic arts
systems
(f lexography
and roto-
gravure


Source
Reactors
Undertread
cementing

Green tire
spraying
Tread-end
cementing

Bead dipping

Tire bui Ming


Printing rollers





Pollutant species
Ethyl acetate,
methanol , chloro-
form, xylene,
benzene, heptane,
toluene
Heptane, hexane,
isopropanol ,
naphtha, toluene
Heptane, hexane,
toluene
Gasoline, hexane,
isopropanol ,
naphtha, toluene
Same as above

Gasoline, hexane,
methanol , naph-
tha, isopropanol,
toluene
Alcohols, glycols,
esters, hydrocar-
bons, ethers,
ketones

Jncontrol led
concentration,
ppm
No data
200-1500°

100-1400C
100-1500°

60-1200C

3-95°


500-2400d




Controlled
concentration
No data
40-300 ppm
(80% reduc-
tion)
10-140 ppm
(90% reduc-
tion)
10-150 ppm
(90% reduc-
tion)
6-120 ppm
(90% reduc-
tion)



50% reduc-
tion




Control
method
Condensers, ad-
sorbers, liquid
scrubbers, incin-
erators
Carbon adsorption
or incineration

Carbon adsorption
or incineration
Carbon adsorption
or incineration

Carbon adsorption
or incineration

Controls not
needed


Waterborne inks




Stream
pressure
Slightly
above or
below
atmos-
pheric
Atmos-
pheric

Atmos-
pheric
Atmos-
pheric

Atmos-
pheric

Atmos-
pheric


Slightly
below
atmos-
pheric
for all
sources
Stream
temper-
ature

65°-85

60°-
110°F
60°- 7t

Ambier

Ambier


Ambie



    (continued)

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TABLE A-l.   (continued)
Storage tanks
 with external
 floating roof

Perchloro-
 ethylene
 dryclean ing
 system
1 	 -

Source
1 	 _ 	



Dryers


Floating roof
1 seal
f
Cleaning machine


Dryer/reclaimer
Distillation unit
vent


Pollutant species
Same as above

Same as above

Same as above
Same as above

Hydrocarbons,
including gaso-
1 ine
Perch loroe thy lene


Same as above
Same as above
-—^
Uncontrol led
concentration,
ppm
500-2400d

500-2400d

500-1500d
500-1500d

Unknown


600-65006


600-6500e
600-65006


Control led
concentration
75% reduc-
tion
75% reduc-
tion
75% reduc-
tion
75% reduc-
tion
Negligible


25-100 ppm


25-100 ppm
25-100 ppm
— =

Control
method
Carbon adsorption

Incineration

Carbon adsorption
Incineration

Roof seal


Carbon adsorption


Carbon adsorption
Carbon adsorption
	 —

Stream
pressure










Slightly
above
atmos-
pheric

Atmos-
pheric

Stream
temper
atur
Amb i e

Ambier

100°-
400°
ioo°-
A flrtO
400 1
Ambie


Ambie
to
120°

Ambi
Ambi
to
12
1
   Reference  23.
   Estimated  on  the  basis  of data from coating of miscellaneous metal parts.
   Reference  21.
   Reference  7.

   Reference  17.

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controlled and  uncontrolled VOC emissions  from these and  other
industries.   It  also shows  sources,  pollutant species,  control

methods, and stream pressures and temperatures.


REFERENCES

 1.  U.S.  Environmental  Protection Agency.  Control  of Volatile
     Organic  Emissions From  Existing  Stationary Sources.   Volume
     II-   Surface  Coating of  Cans, Coils,  Paper,  Fabrics,  Auto-
     mobiles, and Light-Duty Trucks.  EPA-450/2-77-008, May 1977.

 2.  U.S.  Environmental  Protection Agency.  Control  of Volatile
     Organic  Emissions From Existing  Stationary Sources.   Volume
     III:  Surface Coating of Metal Furniture.  EPA-450/2-77-032,
     December 1977.

 3   U.S.  Environmental  Protection Agency.  Control  of Volatile
     Organic  Emissions From Existing  Stationary Sources.   Volume
     IV:    Surface   Coating  of   Insulation   of  Magnet  Wire.
     EPA-450/2-77-033, December  1977.

 4.  U.S.  Environmental  Protection Agency.   Control  of Volatile
     Organic  Emissions  From Existing Stationary Sources.   Volume
     V:   Surface Coating of Large  Appliances.  EPA-450/2-77-034,
     December 1977.

  5  U.S.  Environmental  Protection Agency.   Control  of Volatile
     Organic  Emissions  From Existing Stationary Sources.   Volume
     VI-   Surface Coating  of  Miscellaneous Metal Parts and  Pro-
     ducts.   EPA-450/2-78-015,  June 1978.

  6  U.S.  Environmental Protection Agency.   Control of  Volatile
     Organic Emissions  From Existing Stationary  Sources.   Volume
     VII:    Factory  Surface  Coating   of  Flat   Wood Paneling.
      EPA-450/2-78-032,  June 1978.

  7   U.S.  Environmental  Protection Agency.   Control  of  Volatile
      Organic Emissions From Existing Stationary  Sources.   Volume
      VIII:     Graphic     Arts—Rotogravure     and    Flexography.
      EPA-450/2-78-033,  December 1978.

  8.  U.S. Environmental  Protection Agency.   Control  of  Volatile
      Organic Emissions  From Bulk Gasoline Plants.
      EPA-450/2-77-035,  December 1977.

  9   U.S. Environmental  Protection Agency.  Control  of  Volatile
      Organic Emissions From Storage of Petroleum Liquids in Fixed
      Roof Tanks.  EPA-450/2-77-036, December 1977.
                                A-7

-------
10   U.S.  Environmental Protection Agency.  Control of  Hydrocar-
     bons  From Tank Truck Gasoline Loading Terminals.
     EPA-450/2-77-026,  December 1977.

11.  U.S.  Environmental  Protection  Agency.  Control of Refinery
     Vacuum Producing Systems,  Wastewater Separators,  and Process
     Unit Turnarounds.   EPA-450/2-77-025, October 1977.

12.  U.S.  Environmental  Protection  Agency.  Control of Volatile
     Organic Compounds From Use of Cutback Asphalt.
     EPA-450-2-77-037,  December 1977.

13.  U.S.  Environmental  Protection  Agency.  Design Criteria for
     Stage  I  Vapor  Control  Systems— Gasoline  Service  Stations.
     November 1975.

14.  U.S. Environmental  Protection Agency.  Control  of V°mile
     Organic  Compound  Leaks  From Petroleum Refinery  Equipment.
     EPA-450/2-7B-036, June 1978.

15.  U.S. Environmental  Protection Agency.  Ac.ontfol  Of Volatile
     Organic   Emissions   From  Manufacture  Of  Vegetable   Oils.
     EPA-450/2-78-036.   June 1978.

16.  U.S.  Environmental  Protection Agency.   Control  of Volatile
     Organic  Emissions From Petroleum Liquid Storage in External
     Floating Roof Tanks.  EPA-450/2-78-047, December 1978.

17.  U.S.  Environmental  Protection Agency.   Controlplof- V°lat"e
     Organic  Emissions  From  Perchloroethylene  Dry  Cleaning  Sy-
     stems.   EPA-450/2-78-050,  December  1978.
 18   U.S.  Environmental Protection  Agency.   Control of
      Organic Compound  Leaks  From Gasoline Tank Trucks  and Vapor
      Collection Systems.   EPA-450/2-78-051,  December 1978.

 19.  U.S.  Environmental Protection  Agency   Control °f  Volatile
      Organic    Emissions     From    Solvent    Metal    Cleaning.
      EPA-450/2-77-022, November 1977.

 20   US  Environmental Protection  Agency.   Control  of Volatile
      Organic Em °sVions From Manufacture of Synthesized Pharmaceu-
      tical Products.  EPA-450/2-78-029, December 1978.

 21   U.S. Environmental  Protection Agency.  Control  of ^tile
      Organic   Emissions  From  Manufacture  of  Pneumatic  Rubber
      Tires.  EPA-450/2-78-030, December 1978.

  22  US   Environmental  Protection  Agency.  Air  Pollution  Engi-
    '  neering Manual.   2d.  ed.  AP-40,  1973.
                                 A-8

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23.  U.S. Environmental Protection Agency.   Guidance to State and
     Local Agencies in Preparing  Regulations  to Control Volatile
     Organic  Compounds  From  Ten  Stationary  Source  Categories.
     EPA-450/2-79-004, 1979.
                                A-9

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    REPORTNO
                                      TECHNICAL REPORT DATA
                              (Pirate read Imuruelions ci ifir rtvtnt btfort
  4 TITLE AND SUBTITLE
   Surrmary of Available Portable VOC  Detection Instruments
  7  AUTHQRIS)
   Mazen Y.  Anastas, Herbert J. Bel knap
   PERFORMING ORGANIZATION NAME AND ADDRESS"
  PEDCo  Environmental, Inc.
  1006 N.  Bowen Road, Suite  201
  Arlington, TX  76012
  3 SPONSORING AGENCY NAME AND ADDRESS
  3ivision of Stationary Source  Enforcement
  U.S. Environmental  Protection  Agency
  Washington,  DC   20460
  t SUPPLEMENTARY NOTES
                                                              3 RECIPIENT'S ACCESSION NO
               S REPORT DATE
                 March 1980
                                                              • PERFORMING ORGANIZATION CODE
               8 PERFORMING ORGANIZATION REPORT NO
                PN  3570-3-C
               10 PROGRAM ELEMENT NO.
               11 CONVRACT/GRANT NO
                68-01-4147
                Task Order 120
               13 TYPE OF REPORT AND PERIOD COVERED
                Final
               4 SPONSORING AGENCY CODE
  DSSE Project Officer:   John R. Busik,  EN-341  (202)  755-2560
  t  ABSTRACT
                                                   «
  volatile organi  compound  VOC) emission  so2?ceS   $M?»™ compliance monitoring of
  gathered on the performance character Jtl«  5 Ii«      rep°rt Presents the  information


                                   ^
17
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
Air  pollution
Measuring instruments
Organic  compounds
19 DISTRIBUTION STATEMENT
Unlimited
EPA Form 1220-1 (I 7JJ
                                                IDENTIFIERS/OPEN ENDED TERMS
                                                                           c  COSATI Field/Croup
 RACT compliance
 VOC detection
 VOC emissions
19 SECURITY CLASS (T»,,
 Unclassified
                                               20 SECURITY CLASS (Thu page)'
                                                Unclassified
 13B
 14B
 07C
21  NO Of PAGES
     _46	
21  PRICE

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