-------
Sampling systems for SVOCs must employ a quartz fiber (or other low background)
filter followed by a suitable sorbent media. Also, these systems generally require large air
volumes (e.g., the use of a high-volume air sampler) to achieve the necessary detection limits
for evaluating health risk or action levels for SVOCs.
Even though these samples are collected on combined filter and sorbent media, it
cannot be assumed that separate analyses of the two substrates will yield the relative
particulate-bome and vapor-phase constituent concentrations. Some SVOCs will be
transferred from the paniculate phase to the vapor phase because of the vacuum applied
during the sampling process. The phase distribution depends on the temperature and the
degree of volatility of the individual compound. Techniques for phase distribution analysis
are still being developed. Most of the phase distribution techniques require the use of low-
volume sampling techniques and therefore are not appropriate for many compounds that have
low health effects levels.
Polvchlorinated Biphenvls (PCBs)
PCBs usually are collected using a high-volume PS-1 sampler manufactured by
General Metal Works, Village of Cleves, Ohio. Substrates consisting of a quartz fiber filter
(or similar low background filter) with a solid sorbent consisting of layers of polyurethane
foam (PUF) between a layer of Florisilฎ resin. Foam plugs alone can be used; however,
when using PUF plugs alone, the collection efficiency of mono- and di-chlorinated congeners
may decrease.
Sampling duration should be approximately 24 hours, or 200 cubic meters (m3).
Sample volumes significantly less than 200 m3 may result in diminished detection limits,
while sample air volumes in excess of 275 m3 may result in analyte breakthrough. These
sample volumes will generally be adequate for any Superfund site containing PCB-
contaminated soils. If the known contamination levels are extremely high, lower sample
volumes and/or shorter sampling durations may be used, however, it is probably best to start
3-29
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with the sampling times and volumes outlined and adjust them accordingly as data becomes
available.
A NIOSH method using sorbent tubes for determining PCB concentrations also exists.
This method is similar to the high-volume methods described above in terms of sorbent
media type and analytical method, but it uses small sorbent tubes and low volumes. This
technique was developed to monitor workplace exposure and consequently has detection
limits several orders of magnitude higher than those needed to determine action levels for
community exposure. The techniques may be appropriate for monitoring worker exposure
during remediation, but it should not be used for fenceline monitoring or to determine
compliance with health risk action levels.
Polychlorinated Dibenzo(p)dioxins and Polychlorinated Dibenzo(p)furans
(PCDDs/PCPFs)
Polychlorinated dibenzo(p)dioxins and polychlorinated dibenzo(p)furans
(PCDDs/PCDFs) may be found at Superfund sites either due to their presence in soil from
contamination by organopesticides or their production during the on-site incineration of soil
or waste containing high levels of chlorinated compounds (such as chlorinated solvents).
PCDDs/PCDFs are toxic to varying degrees, depending on the number of chlorine
molecules and the position of those molecules. Generally, only the fifteen 2,3,7,8-substituted
isomers of PCDDs/PCDFs are a major health risk concern; 2,3,7,8-tetrachloro-
dibenzo(p)dioxin (TCDD) is the greatest risk. Although the octa-chlorinated dioxins and
furans are ubiquitous in the environment, they pose little health risk and therefore are seldom
quantitated.
Action levels for 2,3,7,8-TCDD may be on the order of 3.0 pg/m3 to 5.5 pg/m3.18
Action levels are not normally used for the other 2,3,7,8-substituted isomers. To obtain such
low detection levels, very large air sample volumes must be sampled (800-1200 m3).
Samples should be collected on quartz fiber filters (or equivalent) with a PUF plug solid
sorbent using a PS-1 high-volume air sampler. Sample collection duration will be 48-72
3-30
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hours, depending on the analytical technique used to analyze the samples. Sample
breakthrough with PCDDs/PCDFs is not a problem; however, it is important that surrogate
compounds be added to each PUF plug before sampling to determine sampling and analytical
recoveries. The air volume needed will depend somewhat on the analytical technique used to
analyze the samples; the lower value (800 m3) is needed for high resolution gas
chromatography/mass spectroscopy (GC/MS), and larger volumes are required for medium
or low resolution GC/MS.
Organochlorine Pesticides
Organochlorine pesticides can be collected using a low-volume sampling technique,
adsorbing the pesticides on to polyurethane foam (EPA Method TO-10), or they can be
collected using a high-volume technique. Care must be taken when using high volume
sampling techniques because many of these compounds have low breakthrough volumes with
PUF sorbent media. An additional sorbent medium, such as Florisilฎ resin, should be used
in addition to the PUF plugs. When using a high-volume approach, adequate surrogates
should be added to help determine the potential for breakthrough.
The advantage of high-volume sampling is the ability to concentrate more ambient air
and consequently lower the detection limits. Using the PUF along with Florisilฎ resin allows
for the simultaneous collection of both PCBs and pesticides, with the Florisil resin helping to
prevent breakthrough of the lighter molecular weight pesticides.
Polvnuclear Aromatic Hydrocarbons (PAHs)
Polynuclear aromatic hydrocarbons (PAHs or PNAs), can be encountered at many
sites, especially old "Town Gas" sites. PAH compounds range from three to six aromatic
rings and will exist in both the vapor and particulate-borne phases. The percentage of the
compound found in each form generally depends on the molecular weight of the compound
(i.e., the lower the molecular weight the greater the percentage of compound found in the
vapor phase).
3-31
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Like other semi-volatile compounds, PAHs also must be collected with both a
paniculate filter and back-up sorbent media. Several sorbents have been used to collect the
PAHs, including Tenax GC, XAD-2, and PUF. All these compounds have been found to
have a high collection efficiency for benzo(a)pyrene (B[a]P). EPA Method TO-13 specifies
the use of either XAD-2 resin or PUF. Other variants include XAD-2 resin sandwiched
between two one-inch PUF plugs, or XAD-2 resin supported by a one-inch PUF plug. For
the heavier PAHs, any of these techniques should prove satisfactory; however, if lower
molecular weight compounds, such as naphthalene, acenaphthylene, or acenaphthene are to
be quantitated, XAD-2 resin without any PUF should be used. This is due to high
background levels in the PUF material. The XAD-2 resin also has a high background level
of naphthalene; however, typical ambient levels should be well above the background level if
careful cleaning is performed.
As with most of the semi-volatile compounds, samples usually are collected using PS-
1 high-volume samplers. Other low- and medium-volume samplers are also acceptable;
however, the lower the total sample volume, the worse the analytical detection limits. In
some cases, such as when reliable electrical power is not available, battery-operated, low-
volume samplers may be necessary. Sampling periods may need to be extended if low-
volume samplers are used.
A NIOSH method exists that uses filter and sorbent tubes for determining PAH
concentrations. This method is similar to the high-volume method described above in
sorbent media type and analytical method, but it uses small sorbent tubes and low volumes.
The technique was developed to monitor workplace exposure; consequently, the detection
limits are several orders of magnitude higher than those needed to determine action levels for
community exposure. The technique may be appropriate for monitoring worker exposure
during remediation but it should not be used for fenceline monitoring or determine
compliance with health risk action levels.
3-32
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3.1.4 Particulate Matter
Solid or liquid participates (aerosols) can be released from Superfund sites into the
ambient air. These can include contaminated and noncontaminated soil particles, heavy
metal particulates, pesticide dusts, and droplets of organic or inorganic or organic liquids.
Particulate matter (PM) is collected to determine the total or size-fractionated paniculate
matter concentrations, heavy metals concentrations, and/or particulate-borne aerosols/organic
compound concentrations in the ambient environment surrounding a site. Table 3-8
summarizes the advantages and disadvantages of certain paniculate sampling techniques.
Several different sampling devices can be used to collect the samples including real-
time analyzers, low- to high-volume paniculate samplers, and sampling systems that only
collect a certain size fraction of the paniculate matter. Manual collection methods are by far
the most commonly used for measuring both total suspended paniculate (TSP) matter19 and
paniculate matter with an aerodynamic diameter of less than 10 microns (PM10).20 Both
methods require the subsequent analysis of collection filters, a process that can take, at the
very least, 24 hours.
Two types of high-volume samplers are commonly used to collect paniculate matter.
The first collects all airborne paniculate matter and is referred to as a total suspended
paniculate (TSP) sampler, while the second collects only paniculate matter with an
aerodynamic diameter of less than 10 microns (PM10). The PM10 paniculate matter is
important from a health risk perspective, since this size fraction can enter the human
respiratory system because it is too small to be filtered out by the body's defense
mechanisms. At most sites, PM10 will be measured because the results from this analysis can
be directly correlated with potential health effects. If environmental impacts being evaluated,
TSP samplers may be more appropriate.
3-33
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3-34
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Direct reading instruments able to continuously monitor and display ambient air
particulate counts have been available for several years and are increasing in use. They fall
into two classes: optical devices and radiometric devices.
Optical-based paniculate monitors include Transmissometers and Light Scattering
devices. A transmissometer consists of a light source and a detector. By comparing the
obstruction of a light beam by paniculate matter in the sample gas to an unobstructed light
path. These types of monitors are also used for in-situ applications, such as across a stack.
Radiometric monitors measure paniculate matter by a radiation attenuation technique; low-
energy beta radiation is normally used. In the typical beta-gauge, a filter tape is slowly
moved past a radioactive beta source, and the sample is drawn into the sample inlet of the
instrument, where it passes through a tape filter mechanism. The radiometric attenuation of
the filter is then measured before collection in the clean state and after collection in the dirty
state.
Automated paniculate monitors (of either type described above) are able to provide
real or near-real time data of ambient air paniculate concentrations. They are particularly
valuable, therefore, in emergency removal applications, where frequent updates are required.
Automated particulate monitors are more expensive than more conventional paniculate
sampling techniques and, because of their increased complexity, require greater technical
skills by the operators responsible for maintaining them. Also, they must be installed in an
environmentally controlled shelter, making them less amenable to small or short-term
monitoring programs. No information about heavy metal concentrations or other constituents
can be discerned from these monitors.
At many sites where the pollutant of interest is particulate borne (e.g., heavy metals),
portable analyzers can only be used to estimate the potential exposure from the pollutant by
using the particulate value to extrapolate a heavy metal concentration. The action limits set
using these analyzers are usually quite conservative and are generally based on historical data
from high-volume sampling techniques. Portable real-time PM analyzers are available with
detection limits of 1 /zg/m3.11
3-35
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3.1.5 Inorganic Compound Collection Methods
Heavy metals, including lead, arsenic, chromium, cadmium, nickel, and zinc, are a
concern at many Superfund Sites. Mercury and such inorganic compounds such as cyanide
are also encountered frequently. These elements may have vastly differing effects on human
health, depending on the form or compound in which the element exists. An example is the
difference between hexavalent chrome (chrome (VI)) and trivalent chrome (chrome (HI)).
Methods for determining the different forms or valence states of an element or
compound can be labor and time intensive in relation to determining the existence of the base
compound. In many instances, an action level will be based on the concentration of the base
compound (e.g., total chrome) as if it were all in the more toxic form (i.e., hexavalent
chrome). This may hamper remediation efforts if such efforts are curtailed when a "true"
health concern does not actually exist. In this instance, performing the more difficult and
expensive analysis could remove some undue restraints from the remediation effort. Various
methods for collecting the inorganic compounds commonly found at Superfund sites are
discussed below.
High-Volume Sampling For Heavy Metals
As the name implies, high-volume collection methods collect large volumes of air.
Most metal samples are collected on either quartz or glass fiber filter. While either of these
filters can be used, experience has shown that quartz fiber filters provide lower background
levels of compounds of interest and less chance of interferences. Since heavy metals are
associated with paniculate matter in the environment, a decision as to what particulate
fraction to collect must be made.
There are two basic types of high volume samplers those that filter out all
particulate matter in the air sample (TSP) and those that collect a certain size fraction,
normally 10 microns and less (PM10). Particles with an aerodynamic diameter of more than
10 microns aren't generally able to enter the human body because they are filtered out by the
3-36
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body's defense mechanism. Particles smaller than 10 microns are able to enter the body and
therefore pose a greater risk to human health. If a health risk action level based on
respiratory action is being applied, PM10 paniculate matter should be collected. TSP
samplers are appropriate where the potential for land deposition and bio-accumulation is of
concern.
Medium- and Low-Volume Sampling
Medium- and low-volume paniculate sample collection methods are those that collect
less than 10 cubic feet-per-minute; some samplers designed to collect only a few liters-per-
minute. Samplers included in this class include the Dichotomous sampler, the Battelle-
Columbus medium-volume air sampler, and other portable paniculate samplers.
These samplers are generally used for specialty applications (i.e., the Dichotomous
sampler is used to size fractionate ambient paniculate matter) or where large masses of
paniculate matter are not needed for chemical speciation. Also, there are low-volume solar
or battery operated paniculate samplers for use in areas where electrical service is not
available. As a general rule, if electrical service is available, high-volume methods are
generally preferable to low-volume methods when the paniculate matter needs to be
analyzed.
Mercury
Almost all metals can be collected using a high-volume sampling technique. The one
notable exception is mercury. Mercury can exist in several forms, including vapor-phase
elemental mercury, which is the most common form in ambient air. Because of the volatility
of mercury, high-volume filtration techniques are not appropriate for sampling mercury.
From a health effects perspective, the elemental and methylmercury forms are the most
serious. Methylmercury forms when mercury is deposited in freshwater lakes and is
transformed into methylmercury at the water sediment interface. Therefore, methylmercury
should not be of concern at most Superfund sites. Elemental mercury will typically be the
3-37
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primary form. The best methods for collecting mercury involve amalgamating the mercury
with gold. Several researchers, including Gary Glass with the U.S. EPA in Duluth,
Minnesota,20 have used the Jerome mercury analyzer with good results. This analyzer can be
used to determine real-time mercury concentrations and, by using gold foil dosimeters, can
be used to measure time-integrated samples.
Cyanide
The commonly employed methods for determining cyanide involve collecting the
cyanide in basic (either NaOH or KOH) impingers. If both the paniculate cyanide and
gaseous cyanide are to be determined, a teflon filter can be used before the impingers.
Potassium hydroxide (KOH) is the recommended impinger solution; however, sodium
hydroxide (NaOH) can also be used.
3.2 ANALYTICAL METHODS
An overview of analytical methods is given below, followed by a discussion of
specific methods for analyzing VOCs, SVOCs, and PM/Metals.
3.2.1 Overview of Analytical Methods
To a certain extent, the sampling method used to collect the samples will dictate what
analytical methods can be used. In some instances, however, several analytical methods will
be appropriate and a decision as to what method to use will have to be made. Choosing an
analytical method will require a knowledge of the form of the analyte being determined as
well as other factors, including:
Level of quantitation required to meet action levels;
The sample turnaround time;
Anticipated form(s) of the analyte present in the sample; and
Availability and capability of on-site or nearby laboratories.
3-38
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An example of the trade-offs in choosing among analytical methods is the availability
of GC and GC/MS techniques for analyzing both VOCs and SVOCs. For most of the
organic compounds discussed in this section, both GC and GC/MS methods are given. As a
general rule, GC methods coupled with appropriate detectors are more sensitive, in some
cases by several orders of magnitude, than the corresponding GC/MS method. GC methods,
however, all suffer from the potential co-elution of peaks, although using multiple detectors
can help alleviate some of this problem. GC/MS is much more accurate from a qualitative
standpoint, but often is unable to detect compound levels commensurate with pre-set action
levels. Determination of the most appropriate analytical method for each target analyte will
have to be based on site-specific objectives.
This section briefly describes appropriate analytical methods for many compounds
typically encountered at Superfund sites. Real-time monitors, remote sensing
instrumentation, and fixed location continuous analyzers are not discussed in this section,
since their applications are a combination of simultaneous sampling and analytical functions.
A summary of the various analytical methods, along with the advantages and disadvantages
of each, is presented in Table 3-9. The various analytical approaches used in the TO
methods are shown in Figure 3-4.
3.2.2 Volatile Organic Compound (VOC) Methods
This section discusses VOC samples collected in SUMMAฎ polished stainless steel
canisters and those collected on sorbent media. Because of the vast number of sorbents for
collecting VOCs, only general guidance for performing sorbent analysis is given.
Canister Methods
Canister sampling techniques are appropriate for a wide range of volatile organic
compounds. Likewise the two most commonly used analytical techniques for analyzing
canister samples are able to determine a wide range of compounds. These methods are gas
chromatography with multiple detectors (GC/MD) or gas chromatography with mass
spectroscopy (GC/MS). These two analytical techniques are the basis of EPA Method TO-
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3-39
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GC
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Figure 3-4. Compendium of TO Analytical Methods
3-42
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GC/MD uses several analytical detectors either in series or in parallel. Since
selection of the detectors can be based on the compounds present at the site, lower detection
limits or greater specificity for certain compounds can be achieved. An example of this is
the use of a Hall Electroconductivity Detector (HECD) for detecting halogenated compounds.
This detector is capable of detecting many halogenated compounds at ambient concentrations
of 10-100 parts-per-trillion with good precision and accuracy. With either method, some
type of sample preconcentration is required. Normally cryogenic preconcentration is used;
however, sorbent preconcentration with thermal desorption can also be used.
Selecting GC/MD or GC/MS will depend on several factors, including:
The physical characteristics of the compounds to be analyzed;
The number of compounds quantitated; and
The detection levels required (usually driven by health risk criteria).
There are several types of GC/MS systems, and the specific operating mode will affect the
choice of analytical techniques. All GC/MS techniques involve separating a gas sample
using capillary chromatography and basing the identification of compounds on the compounds
mass fractionation. In general, however, all GC/MS techniques suffer for similar problems.
They include:
Sensitivity to water vapor; the samples must be thoroughly dry before analysis;
Difficulty in determining low molecular weight compounds; and
Generally less sensitivity than GC only methods.
GC/MS instruments are typically operated in either full scan mode or in selective ion
monitoring (SIM) mode. SIM is used when a small target list (usually less than 15 target
compounds) of compounds are being quantitated. SIM has the advantage of being
significantly more sensitive than the full-scan mode for most compounds, but cannot detect
ions from other compounds that are not on the target list. Full-scan monitoring provides
more qualitative information, but may not be sensitive enough to determine the health risk
potential of many ambient compounds.
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Because of the number of different detectors available, GC/MD may be preferable in
some instances. GC/MD systems are not as sensitive to water vapor as GC/MS systems;
therefore, they can be used to analyze samples containing polar compounds, which would
typically be removed in the sample drying process. A GC/MD will normally be capable of
detecting significantly lower ambient concentrations than a GC/MS, although SIM may
achieve similar analytical detection limits. When using SIM, however, the ability to detect a
large number of compounds will be jeopardized. GC/MD relies primarily on
chromatographic retention time to determine compound identity. Co-elution of compounds
may cause interference; however, the compound identity can many times be confirmed by the
relative responses for that compound from the different detectors.
Both GC/MD and GC/MS are excellent analytical methods, and each has certain
advantages and disadvantages for specific applications; however, the overall differences
between the two methods are fairly minor. The choice of GC/MD or GC/MS should be
made by an experienced chemist, based on the compounds present at the site, the potential
uses of the data, the project needs, and the necessary detection limits required.
Sorbent Methods
Because of the number of sorbent methods for collecting and analyzing volatile
organic compounds, this section will only deal with general cautions and concerns with
sorbent sampling in general. Sorbent media analysis may involve many techniques, including
gas chromatography with a variety of different detectors and high-performance liquid
chromatography (HPLC). Regardless of the exact analytical technique, all sorbent sampling
has common steps involved in collecting and analyzing the samples. They include:
Drawing ambient air through the medium and adsorbing the analyte(s) of
interest onto the medium;
Preservation of the collected species until analysis can be performed;
Desorption of the analytes of interest from the medium; and
Separation and detection of the target analytes.
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Precautions that need to be taken while VOCs are being collected on the sorbent
medium are discussed in Section 3.1; therefore, sampling precautions are not discussed
further here. Once the sample is collected, two main factors affect the reliable quantitation
of the target species media artifacts and the desorption characteristics of the medium and
analytes.
Media artifacts or background compound levels must be known to adequately
characterize the analytes being sampled. If the background level is large in relation to
ambient concentrations of target compounds, adequately characterizing the target compounds
will be difficult. Also, media artifacts can form during sampling that may co-elute with the
analytes, thereby masking the true analyte concentration. For any sorbent tube sampling,
adequate media blanks must be analyzed to ensure that background levels of the analytes of
interest will not interfere with the method.
Spiked media samples should also be analyzed to ensure that media artifact peaks are
not occurring during sampling. This is done by spiking one sorbent tube with the analytes of
interest and collecting an ambient sample with this tube side-by-side with an unspiked tube.
The spike recovery will be determined by the difference between the unspiked sample
concentration and the spiked sample concentration minus the spike value. In addition to
helping to determine the formation of possible interference compounds during sampling, this
technique also helps to evaluate overall sample collection, desorption, and analysis
procedures.
The other test that must be done on all sorbent tubes is a desorption study.
Regardless of the desorption technique (e.g., solvent extraction, or thermal desorption), the
efficiency of removing the target analytes from the sorbent media needs to be ascertained.
One potential drawback of some sorbents is that they "hang on" to the compounds too
tightly, and removing the targets from the media is difficult. Because of the generally rapid
turnaround required for Superfund monitoring this may not be a problem; however, if
samples are collected and archived, this may need to be considered.
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Desorption studies should be performed by spiking the sorbent medium with the target
analytes and leaving the spike on the medium the same length of time that ambient samples
are on the medium. Then the spikes are handled in the same way as the field samples. If
the data indicate a consistent bias due to desorption efficiency, either internal standards can
be added before sampling to adjust the data, or a factor can be used to correct for the bias
caused by incomplete desorption.
3.2.3 Semi-Volatile Compounds (SVOQ Methods
This section discusses the general methods used to analyze ambient,air samples for
classes of semi-volatile compounds that may be encountered at Superfund sites. The
sampling methods for these compounds have been discussed in Section 3.1.2. In some
instances, only a single method is suited for the analysis of the compounds, in others, two or
more methods may be appropriate. In these instances, the differences in the methods will be
discussed, as will the relative advantages of each method.
Polvchlorinated Biphenvls (PCBs)
There are two generally accepted methods for determining the quantity of PCBs
collected on PUF or on combined PUF/solid sorbent media, gas chromatography with
electron capture detection (GC/ECD) or gas chromatography/mass spectroscopy (GC/MS).
GC/ECD is the analytical method outlined in EPA Method TO-4. This method detects PCBs
by their Aroclor pattern. An Aroclor is a mixture of compounds that make up a commonly
used product. Since various PCBs have historically been used for a variety of purposes, the
individual arochlor can be identified. GC/ECD analysis has the advantage of being fairly
simple and relatively inexpensive to perform. The major drawback of this analysis is the
inability to detect the compounds when such things as incineration or thermal destruction
have degraded the individual Aroclors.
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If PCBs are being remediated at a site using incineration (or some other high-
temperature treatment) on-site, GC/MS must be used to determine if PCBs are present. This
is necessary if the Aroclors are being incompletely combusted, the Aroclor pattern is
destroyed and the GC/ECD analysis would not be able to recognize the characteristic pattern.
Polvchlorinated Dibenzo(p)dioxins/PolYchlorinated Dibenzo(p)furans
(PCDDs/PCDFs)
PCDDs/PCDFs or dioxins and furans have very low health risk action levels (NOEL
of 5.5 pg/m3 for 2,3,7,8-TCDD);18 therefore, the collection and analysis of these compounds
is quite difficult and expensive. It is generally accepted that at least 800 m3 of air sample be
collected for analysis. Analyses should be performed using high resolution gas
chromatography/high resolution mass spectroscopy (HRGC/HRMS); however, if the air
volume is increased to approximately 1200 m3, medium resolution GC/MS may be used.
Dioxins and furans are very heavy compounds and, depending on the molecular
structure of the congener, they can be quite difficult to remove from the PUF medium used
to collect them. It is very important when monitoring for PCDDs/PCDFs that the laboratory
personnel be experienced in this analysis. Because of the very low levels found, laboratory
contamination is a serious problem, especially if the same laboratory is also handling high-
level samples such as those found in contaminated soils.
Because of the risk of losing or of not being able to remove these compounds from
the various media used to collect and clean the samples during the sample collection and
analysis processes, many surrogate compounds must be added at various steps along the
sample collection/sample analysis process. Surrogate compounds are isotopically labeled
compounds that will act similarly to the native compounds but that can be differentiated from
the native compounds because of the mass difference of the isotope. It is not uncommon for
up to 13 surrogate compounds to be added to each sample. The surrogates are used to
correct sample concentrations due to losses from incomplete desorption of the targets and
losses during sample "clean-up."
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Because of the complexity of the sampling and analysis of PCDD/PCDF compounds
and the extremely high level of quality control needed, the sampling and analysis should only
be performed by individuals experienced in this area. Also, care must always be exercised
to prevent contamination or other bias in the sample collection and analysis.
Organochloride Pesticides
The two primary analytical methods for determining concentrations of organochlorine
pesticides in air samples, gas chromatography with electron capture detection (GC/ECD) and
gas chromatography/mass spectroscopy (GC/MS). GC/ECD is by far the preferred method
because of its lower cost and greater sensitivity. GC/ECD has an order of magnitude, or
greater, sensitivity than GC/MS. Compound identification by GC/ECD is accomplished by
using characteristic retention times, compound standards, and second detector confirmation.
Therefore, GC/MS offers greater confidence in compound identification because of the mass
spectra produced during analysis; however, many sample concentrations will be below what
is detectable by GC/MS.
Polvnuclear Aromatic Hydrocarbons (PAHs)
Polynuclear Aromatic Hydrocarbons (PAHs) are generally analyzed by either high-
performance liquid chromatography (HPLC) or gas chromatography/mass spectroscopy
(GC/MS). HPLC methods involve using high-pressure liquid chromatography coupled to
either a fluorescence detector or a combination of a fluorescence and ultraviolet detectors.
Because of the second detector confirmation, this latter method renders highly accurate
results. Also, many fluorescence detectors are capable of being programmed to scan certain
wavelengths for additional confirmation and lower detection limits.
Like the other method comparisons described above, GC/MS is capable of accurate
identification; however, its sensitivity is generally less by an order of magnitude or more.
GC/MS is also more costly than HPLC. Depending on what ambient levels are detected,
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identification of a few samples by GC/MS will help confirm identifications made by the
HPLC analysis.
3.2.4 Inorganic Compound Methods
The inorganic compounds normally found at Superfund sites include heavy metals,
including mercury, and cyanide salts. These analytical methods are discussed in this section.
Heavy Metal Analytical Methods
Filter samples from high-volume samplers are digested in acid and analyzed by one of
several methods. The potential methods include atomic absorption spectroscopy (AAS),
inductively coupled argon plasma emission spectroscopy (1CAPES), and graphite furnace
atomic absorption spectroscopy (GFAAS). These three methods are similar in their
analytical theory, the differences being primarily in the exact technique. The merits of these
methods are discussed below.
Atomic absorption spectroscopy (AAS) involves aspirating an acid-digested filter
sample into a flame, which vaporizes the element of interest. Light of known intensity
characteristic of the element is directed through the metal vapor where it is absorbed. The
absorption is proportional to the concentration over a certain range. This technique is
relatively inexpensive, readily available, and quite sensitive for most heavy metals. Its major
drawback is that only one element at a time can be determined.
Inductively coupled plasma atomic emission spectroscopy (ICP-AES) uses a very
high-temperature argon plasma flame to excite the atoms. 1C APES can be used to detect up
to 40 elements simultaneously, which makes it very cost effective for analyzing samples of
several elements. While these instruments are widely available in laboratories, they are
expensive and may not be suitable for an on-site laboratory because of their cost.
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There are several commonly occurring metals found at Superfund sites that are not
amenable to either AAS or 1C APES. They include notably lead and arsenic. For these
compounds, GFAAS should be used. Although they can be detected by the other two
methods, the sensitivity is significantly better on GFAAS. For instance, the typical
laboratory detection limit for lead by 1C APES is approximately 50 /*g/L, while for GFAAS,
the laboratory detection limit is approximately 5 /xg/L. If very high lead concentrations are
always found, the ICAPES could be used as a more cost effective way (since it could be
done simultaneously with other metals) to determine lead; however, if greater sensitivity is
desired, GFAAS should be used.
Mercury was discussed in the metals sampling section. Although there are other
methods for collecting mercury, the most accurate methods involve amalgamating the
mercury with gold. As mentioned earlier, the Jerome analyzer (which uses gold foil
techniques) can be used quite successfully for sampling and analyzing mercury. Another
technique (which also involves collecting the mercury on gold) uses cold vapor atomic
absorption spectroscopy to quantitate the mercury concentration. This technique measures
the mercury concentration "cold" without using flame or a high-temperature furnace. The
Jerome analyzer flashes the mercury off the gold dosimeter and measures the difference in
conductance before and after flashing.
Cyanide
Cyanide generally refers to all the CN groups in a compound that can be determined
as the CN" ion. Cyanide compounds may be classified as being either simple, in which the
CN group is present as either CN" or HCN, or complex, where the CN group is complexed,
typically to a heavy metal. Generally, simple cyanides are more toxic than the complex, due
to the greater availability of HCN.
It is possible, by selective preparation methods, to differentiate between the simple
and complex forms of cyanide. Simple cyanides may usually be brought into solution by
aqueous dissolution, as in an impinger. Complex cyanides require a more rigorous digestion,
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such as in acid and with a catalyst, to liberate CN for analysis. After the appropriate
preparation of a collected sample, all solutions may be analyzed for CN~ by the methods
described below.
Three commonly used analytical techniques are used to measure cyanide
concentrations. They include:
Cyanide ion-specific electrodes;
Colorimetric procedures using spectrophotometric techniques; and
A titration technique using silver nitrate.
The major drawbacks of the ion-specific electrode include potential interferences,
many of which could easily be present, along with cyanide contamination, at a site. The
interferences include sulfide, chloride, iodide, bromide, cadmium, zinc, silver, nickel,
cuprous iron, and mercury.
The colorimetric method converts the cyanide to cyanogen chloride, complexing the
cyanogen chloride with a pyridine-barbituric acid reagent to form the color, and measuring
the absorbance. This method is fairly sensitive, with a detection limit of approximately 0.02
mg/L. The major interferences include thiocyanates, sulfide, and high concentrations of
cadmium.
The third method involves titrating the impinger solutions with a solution of silver
nitrate in the presence of a silver-sensitive indicator. This method is best suited to higher
levels of cyanide (i.e., more than 1 mg/L in the solution). Sulfides are the major interferant.
The analytical method chosen for cyanide will depend on what other compounds are
also present at the site, since all three analytical methods have interferences. The various
analytical methods are also sensitive to concentration. To get the best mix of sampling time
or volume, along with the appropriate analytical technique, may require some methods
development and trial and error. Again, the review and input of staff experienced in this
type of sampling is recommended as part of the method selection process.
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SECTION 4
QUALITY ASSURANCE AND QUALITY CONTROL
EPA requires that a quality assurance project plan (QAPP) be prepared and
implemented for all environmental measurement programs mandated or supported by the
agency through regulations, grants, contracts, or other formalized means. The main purpose
of the QAPP is to specify the minimum procedures that must be used to ensure that the
accuracy, precision, completeness, and representativeness of the resulting measurement data
are known, documented, and sufficient to achieve the overall goals of the measurement
program. The information for ambient air monitoring (AAM) programs at Superfund sites
may be incorporated into other documents, such as the site Health & Safety Plan or Remedial
Design Documents, rather than as a stand-alone document. For sites where AAM will be
conducted on a long-term basis, however, a separate QAPP for the AAM program is
recommended.
The general principles of quality assurance and quality control are described in
Section 4.1 of this document. Specific guidelines for preparing and implementing QAPPs for
Superfund Air Pathway Assessment Programs appear in Section 4.2.
4.1 GENERAL PRINCIPLES OF QUALITY ASSURANCE AND QUALITY
CONTROL
In the context of this document, as in other EPA reports, the term quality
assurance refers to the entire system of activities, planned or taken, to ensure that the
measurement data are of sufficient quality to meet the overall goals of the program. In this
context, quality assurance includes such things as: quality planning, personnel training,
standardization of procedures, documentation, data validation, and data quality evaluations.
The term quality control relates more specifically to the operational techniques and activities
used to sustain acceptable levels of data quality. Such things as routine instrument checks,
flow rate checks, duplicate samples, blanks, calibration checks, etc., are part of quality
control.
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Detailed guidelines and procedures for achieving quality assurance and quality
control in air pollution measurement systems are given in EPA's five-volume series, "Quality
Assurance Handbook for Air Pollution Measurement Systems".21'25 Although the series deals
primarily with routine air monitoring for criteria air pollutants (SO2, NO2, O3, CO, PM10 and
Pb), the principles of quality assurance given in Volume I of this QA Handbook form an
appropriate basis for designing a quality assurance program for air pathway assessment
activities. Other useful references are EPA's "Technical Assistance Document for Sampling
and Analysis of Toxic Organic Compounds in Ambient Air"26 and "Preparing Perfect Project
Plans".27 Much of the information that follows is drawn from these documents.
The QA handbook and TAD both describe several different elements of quality
assurance that together make up a comprehensive QA program. The individual QA
elements, listed in Table 4-1, are grouped into separate functional units that relate to the
organizational level to which responsibility is normally assigned. These functional units are:
(1) quality assurance management, (2) sampling quality assurance, (3) analytical quality
assurance, and (4) data management quality assurance. The Quality Assurance Project Plan
should address each specific feature of sampling, analytical, and data management quality
assurance. Specific guidance for addressing each of these topics in a QAPP is given in
Section 4.2. QA management deals with the underlying QA principles and structure used to
design and implement the QAPP. A brief discussion of QA management is given below.
4.1.1 Quality Assurance Management
To be effective, a quality assurance program must be thoroughly integrated
with the overall monitoring effort. A prerequisite to achieving this goal is establishment of a
QA policy, objectives, and organizational structure to support the QA program. All
members of the project team must be familiar with the goals and underlying principles on
which the QA program is based. In the most general terms, the objectives of the QA
program should be to ensure that the measurement data are (1) technically sound and
defensible and (2) of sufficient quality to achieve the specific goals of the air pathway
assessment. Whenever practical, one person within the organization should be responsible
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for coordinating all of the quality assurance activities for the measurement program and for
determining whether the objectives of the QA program are being met. To maintain
objectivity, however, the QA coordinator should not be responsible for directly implementing
the specific QA activities associated with data collection and management (i.e., the specific
elements of sampling QA, analytical QA, or data management QA). These responsibilities
should be assigned to other qualified personnel.
After establishing the QA policy, objectives, and organizational structure, a
QA project plan should be developed. The main purpose of the QA project plan is to specify
in advance the actions that will be taken to accomplish the QA objectives. Specific
guidelines and specifications for preparing QA project plans were previously established by
EPA and are discussed with specific regard to the AAM program in Section 4.2. The
structural format of the QAPP (as well as that of all other formal documentation of
procedures, plans, and specifications) should include a system of document control for
managing the organization and distribution of document revisions.
In addition to the QA items described above, QA management also involves
such things as training personnel, evaluating data, conducting quality assurance audits,
preparing quality assurance reports, and taking corrective action. EPA offers an extensive
list of self instructional and other training courses pertaining to QA/QC through their Air
Pollution Training Institute (APTI). For a list of courses or other related information, write
to:
Registrar
Air Pollution Training Institute (MD-20)
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
(919) 541-2401
The remaining aspects of QA management are the key elements of a QAPP, these are
discussed at length in Section 4.2.
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4.2 QUALITY ASSURANCE PROJECT PLAN
Guidelines and specifications promulgated by EPA require that 16 essential QA
elements be addressed by the QAPP.28 The first two of these elements, title page and table
of contents, pertain only to the structure and format of the QAPP; others provide background
information, such as project objectives and measurement approaches, so that individuals not
already familiar with the project can be appropriately informed. Most of the QAPP
elements, however, describe the specific actions that will be taken to ensure that the data are
of known, defensible, and sufficient quality. The 16 essential elements of a QAPP are
described below. Wherever appropriate, guidance is given on how to address these elements
with specific regard to an air pathway assessment (for some topics, specific guidance is given
in other sections of this documente.g., site selection and measurement methods are
described in Sections 2.0 and 3.0, respectively). The QA/QC elements of a long-term A AM
program are illustrated for a "typical" Superfund scenario in Appendix D.
4.2.1 Title Page
In addition to the obvious information, the title page should indicate that the
QAPP has been approved by the project manager, quality assurance coordinator, and either
the remedial project manager or on-site coordinator. Approvals should be shown at the
bottom of the title page by the signatures of the appropriate personnel.
4.2.2 Table of Contents
As part of the system of document control, the QAPP Table of Contents
should specify the number of pages, revision number, and date of last revision for each of
the QAPP sections. A distribution list, indicating all official recipients of the QAPP should
be included at the end of the Table of Contents.
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4.2.3 Project Description
A general description of the measurement program should be included to
provide background information for persons responsible for reviewing the QAPP. The
project description should include: (1) a description of the site and the status of any remedial
activities, (2) the purpose of the measurement program, (3) target analytes and a brief
description of the measurement approach, (4) specific uses of the measurement data, and (5)
scheduled start-up and ending dates of the measurement program.
4.2.4 Project Organization and Responsibility
The QAPP should include an organization chart identifying all of the key
individuals involved in the technical, QA/QC, and managerial aspects of the measurement
program. The specific responsibilities and authorities assigned to each key individual and, in
some cases, their qualifications should also be described. In some cases, it might also be
desirable to indicate the telephone numbers and office or lab locations of key individuals.
4.2.5 Data Quality Objectives
Data quality objectives, in terms of precision, accuracy, and completeness,
must be specified for each primary measurement parameter. These objectives must be
defined in terms of project requirements (not based on the capabilities of the measurement
methods used) as discussed in Section 2.3 of this document. Qualitative objectives pertaining
to the representativeness and comparability of the measurement data should also be
addressed. In addition, a discussion of the ramifications of not meeting the stated DQOs
should be included in the QAPP.
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4.2.6 Site Selection and Sampling Procedures
The QAPP must document the proposed monitoring site locations, and the
rationale for their selection. Whenever practical, site maps and schematic diagrams should
be used to identify specific locations and monitoring configurations. Photographs taken from
each monitoring site showing the ground cover and fields of view in all directions from the
monitoring site, as well as a closeup view of the actual site location, are also recommended.
The QAPP must also include a description of the sampling equipment and
procedures used for each primary measurement parameter. Whenever practical, conventional
EPA sampling protocols such as those described in the various TO Methods should be
employed. If standard methods are used, it is enough to simply reference the method.
However, if standard methods are modified or if alternate methods are used, a description of
the method and the rationale for its selection should be given. The description of sampling
procedures should include any specifications for: (1) preparation, cleaning and certification
of sampling equipment; (2) sample preservation, transport, and storage; and (3) sample
holding times before extraction and analysis.
4.2.7 Sample Custody
A description of all sample custody procedures, forms, documentation, and
personnel responsibilities pertaining to both field and laboratory operations must be included
in the QAPP. Specific items that must be addressed in this regard are: (1) documentation of
procedures for preparing of reagents or other supplies that become an integral part of the
sample (e.g., filters, sorbent media, or reagents); (2) procedures and forms for documenting
the dates, times, locations, and other relevant data pertaining to sample collection and
analysis; (3) documentation of sample custodians in the field and laboratory; (4)
documentation of sample preservation methods; (5) sample labels and custody seals; (6) field
and laboratory sample tracking mechanisms; and (7) procedures for sample handling, storage,
and final disposition.
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The level at which these items should be addressed depends on the specific
scope and objectives of the air pathway assessment. If the results of the air pathway
assessment will be used in litigation, strict chain-of-custody measures, as defined by EPA's
Office of Enforcement, can be required. In other cases, the goals of sample custody can
simply be to maintain the scientific credibility and integrity of the measurement data.
Detailed guidelines for establishing sample custody procedures are given in
Volume II of EPA's QA Handbook for Air Pollution Measurement Systems.22 Key points in
this regard are: (1) all samples must be uniquely identified to ensure positive identification
throughout the test and analysis procedures; (2) all samples must be handled in a manner
suitable to ensuring that there is no contamination or other breach of sample integrity that
might otherwise be caused by leakage, reactive decay, accidental destruction, or tampering;
(3) chain-of-custody forms must accompany all samples from the field to the laboratory or
intermediate storage points, and the chain-of-custody forms should be signed by all persons
who handle the samples along the way; (4) samples should be shipped only by registered
mail or other forms of registered service, and they should be addressed to the specific person
authorized to receive them; and (5) all field notes, laboratory notes, and original calculations
should be saved.
4.2.8 Calibration Procedures and Frequency
The QAPP must include a description of the calibration procedures and the
recalibration frequencies for each measurement parameter and measurement system. If
standard, documented methods are used, simply referring to the method is sufficient.
Otherwise, a complete description of the calibration approach should be given. The
description of calibration procedures should address: (1) the maximum allowable time
between calibrations and calibration checks, (2) the quality and source of calibration
standards (as a general rule, calibration standards should be certified to between four and ten
times the accuracy of the equipment being calibrated), (3) the traceability of standards to
NIST Standard Reference Materials or equivalent Commercial Certified Reference Materials,
(4) the documentation of calibration results, and (5) a statement of the appropriate
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environmental conditions needed to ensure that the equipment is not adversely affected by its
surroundings (e.g., adverse temperatures, humidity, vibration, lighting, chemical emissions,
radio frequency interferences, or electrical voltage fluctuations).
The frequency of calibration should be in accord with any applicable
regulatory requirements or recommendations of the equipment manufacturer. In the absence
any such guidance, an initial calibration interval should be determined, based on the inherent
stability, precision, bias, and degree of use of the equipment. The time interval may then be
shortened or lengthened, depending on the consistency of results obtained from successive
calibrations.
4.2.9 Analytical Equipment and Procedures
Officially approved EPA analytical procedures should be used whenever they
suit the particular scope and objectives of the air pathway assessment. In these situations,
the applicable method should be referenced in the QAPP. Section 3.0 contains a list of
standard methods that might apply to the air pathway assessment. If standard methods are
modified or alternative methods employed, the modifications or alternate methods must be
described and the rationales must be given for their selection. Whenever modified or
nonstandard methods are used, they must first be validated to demonstrate their performance
characteristics in terms of accuracy, precision, detection limit, and specificity. Procedures
and acceptance terms for the method validation study should be described in the QAPP.
4.2.10 Data Reduction. Validation, and Reporting
A description of the data reduction, validation, and reporting procedures for
each primary measurement parameter must be included in the QAPP. These procedures
should specify: (1) all equations and statistical approaches used to reduce the measurement
data, (2) the method for treating blanks during data reduction, (3) the method for treating
cases of undetected compounds in the statistical calculations, (4) the methods used to identify
and treat outliers, (5) the criteria for flagging and validating data, and (6) the units for
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reporting results. A flow chart is sometimes helpful for depicting the series of specific steps
taken from initial data collection, on through data reduction, validation, reporting, and final
storage. Specific guidance for reducing, validating and reporting measurement data is given
in Section 5.0.
4.2.11 Internal Quality Control
Internal quality control checks should be performed on all sampling and
analytical systems to verify and document whether such systems are operating within control
limits or require corrective action. The procedures, control limits, corrective actions, and
frequencies with which QC checks should be performed should be specified in the QAPP.
Items to be considered as part of internal quality control for field sampling systems include:
flow rate checks; leak checks; timer checks; and visual inspections of sample lines and inlets
for cracks, moisture, or debris. Whenever practical, these checks should be conducted
immediately before and after each sample collection period. The procedures for conducting
QC checks are likely to be instrument-specific. Equipment manuals or EPA-approved
Standard Operating Procedures (e.g., TO Methods) should be consulted for specific guidance
on designing internal QC procedures.
Examples of items to be considered as part of analytical internal quality
control are: system blanks, replicate analyses, surrogate samples, spiked samples, reagent
checks, and calibration checks. A listing of QA/QC samples is given in Table 4-1. These
checks can be used to provide immediate feedback for identifying whether the analytical
systems are operating within pre-established control limits. If control limits are exceeded,
corrective actions should be implemented before additional samples are analyzed. Analytical
control checks should be performed at least once a day, or after every 10 samples are
analyzed.
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In addition to sampling and analytical control checks, quality control samples
should also be collected and analyzed to evaluate the overall performance of the measurement
system. Types of quality control samples include: field blanks, field duplicates, and field
matrix spikes. Note that these types of samples differ from the analytical control samples
described above in that they originate at the field site and therefore reflect the combined
performance of both sampling and analytical systems. Field QC samples therefore provide a
more representative way to evaluate overall data quality, but because of lag times between
collection and analysis they are not as effective as analytical control checks for identifying
the need for corrective action. The recommended frequency for collecting each type of field
QC sample is one per sampling event. Less frequent sample collection is sometimes
acceptable, but the total number obtained during any given period should be at least 5 % of
the total number of ambient samples.
Whenever appropriate, control charts should be used to depict trends in the
QC data, distinguish patterns of random variation from variations of assignable causes, and
identify when the measurement system is out of control.rcf Determinations of appropriate
control limits should be based on either the performance characteristics of the measurement
system or on the specified requirements of the measurement procedure. Common practice
sets control limits at ฑ 3 standard deviations (excluding outliers) from the mean of previous
measurements. Appendix H of The QA Handbook, Volume I, gives detailed guidelines for
control charting QC data.21
4.2.12 Performance and System Audits
Performance and system audits are the primary method to determine if the QA
goals and objectives have been met. The scope and schedule for auditing each primary
measurement system or parameter, as well as the personnel conducting the audits, must be
specified in the QAPP. Performance audits are used to quantitatively evaluate the accuracy
of the data being generated, typically by evaluating the recovery of certified reference
materials through the sampling and analytical systems. System audits address, in qualitative
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terms, the capabilities of the measurement system for generating data that meet QA
objectives for representativeness and comparability. Such things as adherence to established
sampling and analytical procedures, sample custody, and equipment maintenance should be
addressed in a system audit.
To maintain objectivity, performance and system audits should be conducted
by the project's QA Coordinator or other individuals who are not responsible for the
operational aspects of the air pathway assessment. All materials and supplies used in the
audit should also be different from those used during routine operation and calibration of
equipment. Performance audits should be conducted at least once every three months for
long-term AAM networks; however, a more frequent schedule is recommended if results are
highly variable from one audit to the next. A system audit should be conducted before or
shortly after the system becomes operational and should be repeated regularly thereafter
(e.g., quarterly or semi-annually).
4.2.13 Preventive Maintenance
The following types of preventive maintenance should be considered part of
the quality assurance program and addressed in the QAPP: (1) a schedule of important
preventive maintenance tasks that must be carried out to minimize instrument downtime, and
(2) a list of any critical spare parts that should be on hand to minimize instrument downtime.
Preventive maintenance tasks and spare parts are instrument-specific. Equipment manuals
and EPA-approved SOPs should be consulted for guidance on establishing specific
procedures and schedules.
4.2.14 Procedures Used to Evaluate Data Precision. Accuracy and Completeness
Specific procedures used to evaluate data quality in terms of the precision,
accuracy, and completeness of all primary measurement parameters must be described in the
QAPP. These procedures should specify the methods used to gather data for evaluating the
precision and accuracy and all equations used in subsequent calculations. Specific
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requirements for evaluating the quality of the data generated by criteria air pollutant
measurement systems are given in the Code of Federal Regulations and other EPA guidance
documents.9'30 These methods are not always adaptable to air toxics measurement systems,
but whenever practical they should be applied. These and alternative procedures for
evaluating data quality are described below. Note that data quality must always be
determined in a manner compatible with established data quality objectives.
Recommended procedures for determining precision and accuracy depend on
whether the measurement method involves automated on-site analysis or requires integrated
sampling subsequent analysis off site. For automated on-site analytical systems, precision
data should be obtained by periodically (e.g., daily or weekly) challenging the analyzer with
a gas standard of known concentration and observing the analyzer's response. Calculation
procedures given in the Federal Register (Part 58, Appendix B) are used to express precision
in terms of the upper and lower probability limits of the percent differences between the
known and observed concentration values. Although EPA requires these procedures for
certain types of criteria air pollutant monitoring systems, no specific requirements exist for
air pathway assessments. An alternative expression for precision, in this case, is the relative
standard deviation (i.e., standard deviation divided by the mean, expressed as a percentage)
of successive precision check results.
Procedures for determining the accuracy of automated on-site analytical
systems should be similar to those for determining precision, except that the assessment must
be performed by someone other than the operator or analyst who conducts the routine
monitoring and must be performed using gases made from different working standards.
Accuracy should be expressed as the percentage difference between the known and observed
concentration values. Alternatively, accuracy can be expressed as the percent of the known
concentration recovered through the analytical system (i.e., the observed concentration
divided by the known concentration, expressed as a percentage).
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For measurement methods that require integrated sampling and off-site analysis
(these methods are sometimes referred to as manual methods), duplicate (collocated) sample
results should be used for determining data precision. To obtain precision data, collocated
samplers should be located at the site with the highest expected concentration levels of target
analytes. Duplicate samples can be also obtained at alternating sites if portable or multi-
channel samplers are used. Equations for expressing precision in terms of the upper and
lower probability limits of the percent difference of duplicate sample results are given in the
Federal Register (Part 58, Appendix B). Alternatively, precision can be expressed as the
relative percent difference of duplicate sample results, or pooled standard deviation.1*
Accuracy determinations for manual methods should be performed by spiking
sampling media with known quantities of target analytes and measuring their recovery
through the extraction and analytical systems. Media spikes should be prepared by the QA
Coordinator or another individual not involved in the operational activities associated with
sample collection or analysis. The accuracy of the measurement data should be expressed as
the percentage of the spiked amount recovered in the analysis.
Data completeness for both automated and manual methods should be
expressed as the percentage of valid data relative to the amount of data that was expected to
be obtained under correct normal conditions.
4.2.15 Corrective Action
A plan for initiating and implementing corrective actions must be included in
the QAPP. The plan should specify: (1) conditions that will automatically require corrective
actions; (2) personnel responsible for initiating, approving, implementing, and evaluating the
resolution of corrective actions; and (3) specific corrective action procedures used when
predetermined control limits are exceeded. Corrective actions are usually instrument-
specific. Equipment manuals and EPA-approved standard operating procedures should be
consulted for guidance on establishing specific corrective action procedures.
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4.2.16 Quality Assurance Reports to Management
The QAPP should define a mechanism for periodically reporting to
management on the performance of the measurement systems and data quality. At a
minimum, QA reports should include: (1) assessments of measurement data accuracy,
precision, and completeness; (2) performance and system audit results; and (3) significant
QA problems and recommended solutions.
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SECTION 5
DATA MANAGEMENT
The goal of ambient air monitoring (AAM) programs at Superfund sites is to
generate accurate, verifiable reports on ambient concentrations of air pollutants in the area of
concern. These data are usually applied to evaluations of the risk to on-site personnel and
the surrounding community. The data used in these evaluations must be defensible and must
meet the criteria established in the Quality Assurance Project Plan (QAPP) or AAM Plan for
accuracy, precision, completeness, and representativeness. Therefore, establishing sound
data management procedures and objectives early in the program can be critical to its
success.
Long-term AAM programs may generate tremendous amounts of data. In
most cases, AAM data are reviewed regularly (e.g., daily) and compared with action levels
to see if any exceedances have occurred. The AAM data are then stored in hard-copy form,
entered into databases, or summarized in word processing software. Frequently, problems
arise when, at some future date, someone needs to review or use the data. In too many
cases, the data record is incomplete, the data are stored in a variety of formats, or they have
not been consistently validated. It may then be expensive or impossible to reconstruct a
complete set of validated data; therefore, a data management program should be established
before any long-term AAM program begins. Much of the information in this section also
applies to short-term AAM programs.
The key elements of data management for AAM programs include: data
management planning, data acquisition, data reduction, data validation, and data reporting.
These elements are discussed in the following sections.
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5.1 DATA MANAGEMENT PLANNING
Collecting and maintaining unnecessary or redundant data can create needless
data management costs, while insufficient, improperly formatted, or poorly managed data can
prove equally costly to the program. To maximize the efficiency of the data management
process, data collection methods and standards should be developed early in the program
with the end use of the data in mind. Specific information management objectives may
require the comparison of data with chemical-specific health criteria, state or local air toxics
guidelines, ambient air standards, or other compliance requirements. Monitoring results may
be applied to health risk assessment models to calculate the individual or community health
risks associated with ambient air pollutants, or they may be used to validate predictive
software models.
The QAPP or the AAM plan should provide a management framework to
coordinate and evaluate data management program activities. Data management procedures
should be contained or referenced in these documents to ensure that sampling and analytical
data are captured, stored, and maintained in an efficient and secure environment and that the
quality of the measurement data is high enough to meet the goals of the program. Program-
specific information for documentation and recordkeeping requirements, data quality
objectives, and data storage, transfer, and manipulation should be specifically addressed.
Documentation and Recordkeeping
The sampling plan or the QAPP should specify the data recording procedures
for the AAM program. Data must be collected and supporting documentation maintained
for:
Periodic readings of meteorological conditions at appropriate time
intervals;
Temperature, flow rates, volumes and other measured parameters at
specified time intervals;
Instrument operating variables;
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Upset conditions, such as emergency releases;
Calibration or maintenance procedures; and
Sample tracking and analytical results.
A logbook should be maintained for the entire sampling program to document
sampling descriptions, meteorological data and upset conditions. Logbooks should be
maintained for each instrument to record calibration and maintenance activities. Data sheets
and forms should be designed to support raw data collection and chain-of-custody
information. Documentation of analytical procedures and results must also be developed and
maintained throughout the life of the program. Responsibility for maintaining and storing
program documents should be clearly specified to facilitate the rapid retrieval of information.
Data Quality Objectives
Data quality objectives (DQOs) and procedures for evaluating data quality are
specified in the QAPP to ensure the representativeness, completeness and comparability of
measurement data. Acceptance criteria for accuracy, precision, and completeness must be
specified for each primary parameter. Corrective action methods for addressing
measurements not meeting stated DQOs should be addressed, as well as standard statistical
and analytical procedures for manipulating the measurement data.
Data Transfer. Storage and Reporting
Data management procedures for the typical AAM program are characterized
by the need to store and integrate large volumes of data derived from a variety of data
sources. Because these data may be collected over a long period of time by different parties,
developing an integrated data management system for the transfer, storage, and manipulation
of data to create final reports is an essential program planning activity.
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The integration and management of AAM program data are typically supported
by a central, integrated database system. The design and structure of the supporting software
should be compatible with program objectives and, at a minimum, should offer:
Storage for all required data;
Interfaces for accessing or entering field and laboratory information;
The ability to retrieve data in the form of standard or user-specified
reports.
In most cases, the database system must be developed or modified from an existing system to
support the unique needs of the program. Table 5-1 summarizes the topics of concern when
developing databases for AAM programs.
5.2 DATA ACQUISITION
Figure 5-1 depicts a data flow diagram for a typical AAM program. Field-
based data acquisition systems and sampling methods are predefined in the QAPP or
sampling plan. In a well-structured data acquisition environment, automatic interfaces with
the central database are present to reduce data handling costs. In current AAM programs,
monitoring systems may be linked to the central database via modem or another electronic
interface. Sampling information and analytical results are often keyed into the system from
hard-copy data sheets. In some cases, raw or analytical data may also be transferred via
diskette or other electronic medium, and the data are electronically imported into the central
database.
The efficiency of the data acquisition process depends directly on the
compatibility of sample numbering schemes, data element definitions, data formats, and units
of measure for each priority parameter. Standardization of these items facilitates data
transfer, reduces data acquisition costs, simplifies data reduction and validation activities, and
ensures the defensibility of the final reports.
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Table 5-1.
Database Development Issues
lIC-iE^Pri^ii
Data Volume
Data Structures
Data Relationships/
Indexes
Data Redundancy
Data Formatting
Meaning of Fields
Documentation
;;%$$^e Results
Data volume
exceeds expectations
Incorrect design
Design not
optimized for
program data
Existence of
duplicate data
Data inconsistency
Fields incorrectly
defined or having
multiple definitions
Inadequate/poorly
maintained
Polsnfial-lH^iils
unacceptable response times
excessive resource utilization (update time, disk space)
inflexibility
poor performance
increased storage
update problems
false interferences
inefficient updates
complex reporting
poor interactive response
inefficient data retrieval
error-phone reports
complex updates
increased data volume
increased maintenance costs
impedes data transfer
inefficient data comparison/manipulation
error-phone reports
loss of data integrity
incorrect interferences
programming errors
poor program communication
vulnerable to staff turnover
miscommunication between staff
programming errors
expensive maintenance
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Validation Steps
Level I
Level H
Level m
Data Flow
Data Acquisition
Reduction
Validation
Central Database
Reduction
Validation
Data Reporting
QA/QC Procedures
Calibration Maintenance
Inspection Sampling Plan
Data Management
QA/QC
Figure 5-1. Simplified Data Flow Diagram for AAM Programs at Superfund Sites.
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5.3 DATA REDUCTION
Data reduction is the manipulation of raw data, by averaging, integration, and
statistical methods, to create intermediate products for analytical applications and assessment
reporting. Each phase of data reduction is accompanied by a parallel data validation step to
ensure the early detection and resolution of data anomalies.
In AAM programs, data reduction is an ongoing process that begins with the
field instrumentation and supporting data processors that automatically average measurement
parameters for specified time intervals. Laboratory methods for analyzing samples generate
individual sample data (e.g., the integration of a chromatographic peak) by manual analysis
or the use of supporting software tools. These type of data reduction activities are validated
by QA/QC activities for instrument calibration and maintenance and program-specified
laboratory methodologies (see Figure 5-1).
Loading field and laboratory data into the central database may require
additional data treatment to meet database requirements for units, data formats, etc. Data
compatibility issues can be resolved with preprogrammed conversion routines. These
activities begin what is typically viewed as the 'data management' portion of the project and
are integrated with field and lab QA/QC activities specified for the program, as shown in
Figure 5-1.
Once loaded into the central database, raw data should be stored for the life of
the program. For long-term AAM programs, raw data may be periodically archived for
database maintenance. In all cases, the maintenance of raw data files should be supported by
regular backup procedures. These data, once validated, are further reduced to create data
summaries (intermediate data) and final reports.
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Data reduction procedures involve the application of standard statistical
methods for averaging, establishing minimum and maximum values, generating standard
deviations, etc. Statistical calculations for determining ambient concentrations of air
pollutants are complicated by the limitations of existing measurement methods, which operate
within detection limits above those of actual concentration values. For samples characterized
as "not detected" the conventional practice is to substitute such value with a value one-half
the detection limit. This may, however, result in erroneous or unacceptably high estimates
of risk if a number of toxic or carcinogenic compounds are among the target analytes. This
effect is exacerbated if the number of "not detected" values make up a significant portion of
the data set.
5.4 DATA VALIDATION
Data validation is the systematic review of measurement data for outlier
identification or error detection. Suspect values are deleted or flagged by manual or
automated data validation methods. The term "validation" typically implies those activities
performed upon collected data. Validation is distinguished from the quality control activities
that prevent bad data from being collected.
There are three general levels of validation in A AM programs:
Level I validation involves validity checks of raw monitoring data;
Level n validation ~ the independent evaluation of analytical results by
a qualified person; and
Level HI ~ a review to identify data outliers and anomalies.
Level I validation activities involve reviewing chain-of-custody forms to detect
any problems with sampling equipment, canister leakage, etc. that might have contributed to
nonstandard sampling intervals, insufficient sample volume, or other problems that may
negate the sampling event or create questionable results. For monitoring systems, validation
of the raw data is inherent in quality control procedures for calibration and maintenance.
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Level II validations verify preliminary compound identifications, confirm that
analytical systems are operating within acceptance criteria, and identify anomalies associated
with any analysis that might undermine compound results. These activities are performed by
a qualified chemist or air specialist and are designed to ensure that the data criteria for each
analyte are met. Suspect data are deleted or flagged for resolution; measurement bias,
system contamination, or the lack of reproducibility of measurement data may be reasons to
judge the data invalid.
In Level III validation, the data are screened for outliers, concentrations
inconsistent with historical measurement trends, or measurements that are incompatible with
prevailing wind conditions. The validation activities should attempt to correlate any data
anomalies with treatment process conditions or on-site activities. Level III validation
typically occurs with data stored and reduced in the central database system and is supported
by manual review or automated data validation routines.
Acceptance Criteria
The process of data validation ensures that the DQOs for each measured
parameter are met. A key acceptance criterion is the data recovery rate, which expresses the
number of valid observations as a percentage of total possible observations. Data recovery
rates are typically 80% for air quality data and 90% for meteorological data, based on 1990
EPA recovery standards established for permitting purposes.
Section 1.4.17.2.1 of Volume I of the Quality Assurance Handbook for Air
Pollution Measurement Systems,21 contains detailed information on data validation and
screening procedures. In this document, data validation procedures are subdivided into four
general categories:
Routine check and review procedures;
Tests for internal consistency of data;
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Tests of consistency of data sets with previously analyzed data sets
(historical or temporal comparisons);
Tests of consistency with data sets collected at the same time or under
similar conditions.
Table 5-2 summarizes the specific criteria for screening meteorological data,
extracted from "On-Site Meteorological Program Guidance for Regulatory Modeling
Applications,".28
Air monitoring data validation should include evaluating collocated station
results and audit results to determine data precision and accuracy, as described below.
The percent difference between the air concentrations measured at
collocated samplers is:
d = Yi-Xi x 100
where:
d,
the percent difference between the concentration of air toxic
constituents Yj measured by the collocated monitoring station
and the concentration of air toxic constituent X;, measured by
the monitoring station reporting the air quality.
The average percent difference dj for the monitoring period is:
d. = 1 E d
j n ,-=i l
where:
n
percent difference defined above, and
number of samples collected during the monitoring period.
The standard deviation S,- for the percent differences is:
1
n-1
n 2
S d f
1
n
n f
S dj
/ .
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Table 5-2.
Suggested Meteorological Data Screening Criteria*
Meteorological
Variable
Screening Criteria1
Wind Speed
Is less than zero or greater than 25 m/s;
Does not vary by more than 0.1 m/s for 3 consecutive hours; and
Does not vary by more than 0.5 m/s for 12 consecutive hours.
Wind Direction
Is less than zero or greater than 360ฐ;
Does not vary by more than 1 ฐ for more than three consecutive hours; and
Does not vary by more than 10ฐ for 18 consecutive hours.
Temperature
Is greater than the local record high;
Is less than the local record low; (The above limits could be applied on a monthly basis.)
Is greater than a 5ฐ change from the previous hour,
Does not vary by more than 0.5ฐC for 12 consecutive hours.
Temperature
Difference
Is greater than 0.1 ฐC/m during the daytime;
Is less than -0.1ฐC/m during the nighttime; and
Is greater than 5.0ฐC/m or less than -3.0ฐC/m.
Dew Point
Temperature
Is greater than the ambient temperature for the given time period;
Is greater than a 5ฐC change for the previous hour;
Does not vary by more than 0.5ฐC for 12 consecutive hours; and
Equals the ambient temperature for 12 consecutive hours.
Precipitation
Is greater than 25 mm in one hour;
Is greater than 100 mm in 24-hours; and
Is less than 50 mm in three months.
(The above values can be adjusted base on local climate.)
Pressure
Is greater than 1,060 mb (sea level);
Is less than 940 mb (sea level); and
(The above values can be adjusted for elevations other than sea level.)
Change by more than 6 mb in three hours.
'Some criteria may have to be changed for a given location.
SOURCE: Reference 28
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The 95-percent probability limits for precision are:
S,
Upper 95 % Probability Limit - ^ + 1.96
v/2
S,
Lower 95% Probability Limit - d - 1.96 -J-
The accuracy is calculated for the monitoring period by calculating the
percent difference dj between the indicated parameter from the audit
(concentration, flow rate, etc.) and the known parameter, as follows:
d - i-li x 100
where: Yt = monitor's indicated parameter from the i* audit check; and
X; = known parameter used for the r* audit check.
These results should then be compared with the QA/QC criteria stipulated in
the monitoring plan to determine the validity of the data.
Resolution of Data Concerns
To support the resolution of data anomalies, records should be maintained to
track raw data as it is reduced and validated to create intermediate data sets and reporting
summaries. At any stage in this process, data flags may be appended to a measurement.
The specific methods for flagging data may be manual or automatic; they depend on the
program design and the sophistication of supporting software tools. Flags appended to data
during validation may be reclassified or removed after the specific issues for that data point
have been resolved in accordance with the corrective action procedures established for the
program.
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5.5 DATA REPORTING
Meteorological and air monitoring data summaries are prepared from validated
database files. These reports summarize data for airborne pollutant concentrations at sample
locations and facilitate the determination of exposure potentials.
Meteorological Pafo Summaries
Meteorological data summaries should contain at least the following
information:
Hourly averages for all meteorological parameters for the sampling
period;
Summary wind roses, including daytime and nighttime wind roses (for
coastal or complex terrains);
Data recovery summaries for each measured parameter;
Summary of dispersion conditions for the sampling period;
Tabular summaries of means and extremes for temperature and other
parameters.
It is recommended that sequential hourly data be derived for the summary
reports to keep data volumes down and avoid undue complications in evaluating the data. A
one-hour time frame is enough to account for temporal variabilities in the measured
parameters. For multistation sites, it may be useful to format the data in adjacent columns to
facilitate manual comparisons. Data recovery target standards are 90% for meteorological
parameters and are an initial reflection of data completeness and representativeness.
Statistical summaries by month, year, season, and for the monitoring period
can be derived from the meteorological data summaries. Figure 5-2 depicts a useful format
for representing wind rose summary data. For sites with diurnal wind patterns, separate wind
rose summaries for daytime and nightime conditions are recommended.
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WIND ROSE
N
7.0
Wind Speed
(mph)
0 PcL
SJJPct
lOJJPct
Pet Calms - 4.68
December 1, 1991 - November 30, 1992
Figure 5-2. Sample Wind Rose Diagram
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Air Data Summaries
Air data summaries list the concentrations of all monitored constituents
by station and monitoring/sampling period. The summarized data should include method
detection limits, undetected compounds, and upwind/downwind exposure classifications.
Operational data for monitoring stations, such as sample flow rates, station numbers, and
sampling duration should also be reported.
For each measured constituent at each monitoring station, the following data
should be presented:
Total number of samples;
Data recoveries (target 80%);
Mean, median, minimum, and maximum concentrations;
Detection limits;
Frequency above and below detection limits;
Number of exceedances for QAPP-selected values; and
Upwind and downwind exposure summaries.
The standard unit of measure for reporting air concentrations is micrograms
per cubic meter, or parts per billion (ppb). It is also useful to include raw data used to
derive concentration values, such as the duration of sampling event (unit time); the volume of
sampled air (cubic meters); the temperature (degrees Fahrenheit); the pressure (mm Hg); and
constituent content in the sample (micrograms). Upwind and downwind summaries, such as
those shown in Figures 5-3 and 5-4, should be included for each monitoring station to
support data interpretation. Upwind conditions are applied to background characterization,
and concentrations measured downwind are applied to source-specific exposure assessments.
Further analyses or statistical treatment of these basic data are carried out to
derive information for sample event and results summaries; relationships between sample
events, unit operating efficiencies and meteorological conditions; and comparisons with
background levels and other air emission sources. The air monitoring data summary
typically includes a narrative discussion of sampling results and conclusions about the quality
of the data set according to established data quality objectives.
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6H
i i i i i i i i I i i i i
Parent Downwind (%)
Figure 5-3. Regression Equation of Concentration versus Percent Downwind Overlayed
with 95% Confidence intervals for the Mean
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Reports
Data summaries are further reduced and validated to present statistical reports
for the monitoring period and for monthly, seasonal, and annual ambient conditions. The
information in final reports is used to support data interpretation and program decision-
making. Concentration means and extremes, exceedances of health and safety criteria and
other selected compliance thresholds, and data quality summaries are typically included in
annual or final reports. These reports should be reviewed by knowledgeable individuals to
validate the summary conclusions and to ensure that the data are accurately represented to
avoid the possible misinterpretation of reported results
Data from AAM reports are often used to augment and validate air dispersion
models, which aide in the interpretation and extrapolation of ambient concentration data to
unmonitored on and off site locations. These data can be applied to health risk assessment
models to determine the risk of exposure of site personnel and the surrounding community.
5.6 DATA USAGE
Ambient air monitoring data may be generated from a variety of sampling
locations at Superfund sites, including personal (IH) samplers, and samplers situated at the
work zone, site perimeter (fenceline), and off-site near sensitive receptors. These data may
have several uses. The most common usage is to compare the measured air concentrations
with short- or long-term action levels. Comparisons with short-term action levels can be
done directly with individual data points. Any exceedance of short-term action levels may
indicate that adverse exposures have occurred. Comparisons with long-term action levels can
be done with individual data points, but more meaningful comparisons are made using data
averages developed from weeks or months of data. Any exceedances may not necessarily
indicate a problem, because long-term action levels typically are based on lifetime exposures.
If the data trends show a consistent pattern of exceeding the long-term action levels, then
some remedial action may be warranted.
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Ambient air monitoring data frequently are used in conjunction with dispersion
modeling results. The AAM data can be used to validate the model outputs for the specific
site of interest. This is done by comparing measured ambient air concentrations to the
concentrations predicted by an atmospheric dispersion model that uses the actual
meteorological conditions present during the monitoring. Dispersion models are inherently
conservative, so the model output will usually overpredict ambient concentrations. The
degree to which the model over (or under) predicts will depend on site-specific factors. The
degree of overprediction observed for the short-term dispersion modeling may be used, with
limitations, as a correction factor when interpreting long-term dispersion modeling results.
All of the above discussion, of course, assumes that the source term (i.e., emission rate) for
the site is known.
AAM data can, under ideal conditions, be used to generate a source term for a
site. This is done by modelling a unit emission rate (i.e., 1 g/sec) and ratioing the estimated
downwind concentrations to the actual measured concentrations (measured/estimated). This
ratio can then multiplied by the unit emission rate to yield a source term. If multiple sets of
AAM data versus model output show a consistent ratio, then the estimated source term can
be assumed to have less uncertainty than a ratio derived from a single data set. It may be
difficult or impossible to estimate a source term using AAM data if multiple emission sources
exist at the site, if the emission rate varies over timeframes that are shorter than the AAM
duration, or if there are upwind emission sources.
AAM data obtained from OPM systems usually are in path-weighted units of
ppm*meter or ug/m2 and, therefore, are not directly comparable to typical action levels or
health standards that are given in units of ug/m3 or ppm. This does not mean that the OPM
data are not usable, only that the OPM data may require further data reduction before
comparisons can be made. The most common data treatment is to divide the OPM data by
pathlength to yield a path-averaged concentration (in ppm or ug/m3) along the path that is
monitored. This average concentration is analogous to an average obtained from a line of
point samplers. The OPM data, however, can not be used directly to determine if the mass
of emissions was equally distributed along the beam path or if there were localized "hot
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spots" of relatively high air concentrations. Such information can be obtained only if
multiple OPM configurations are used; for example, different path lengths could be used and
the measured concentrations compared to identify when contributions from any hot spots are
observed.
OPM data also can be used to back-calculate a source term using one of
several methods. If the emission plume is fully contained within the beam path, one need
only determine the vertical dispersion to calculate the source term (see Reference 5). The
vertical dispersion can be evaluated using a vertical array of point samplers, or it may be
extrapolated from measurement of the wind direction standard deviation (sigma theta) by
using Pasquill-Gifford stability classes and the associated dispersion curves. A second
method is to use a tracer gas on the site. The tracer gas is released at a controlled rate. The
path-weighted concentration of the tracer is measured at a downwind line. The simplest
method of calculating a source term using a tracer gas is to ratio the measured concentrations
of the tracer gas and the compound of interest and use this as a multiplier to the known
emission rate of the tracer gas to obtain the emission rate of the compound of interest. This
approach is limited by the degree to which the tracer release approximates the emission
source and, in some cases, by differences in atmospheric transport between the tracer gas and
the compound(s) of interest.
5-19
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SECTION 6
ESTIMATION OF PROGRAM COSTS
The costs associated with conducting ambient air monitoring (AAM) at
Superfund sites will depend on a number of issues, including:
Objectives of the monitoring program;
Target analyte list;
Frequency of monitoring; and
Duration of the AAM program.
The objectives of the AAM program will dictate the costs. Usually,
monitoring objectives will involve some combination of documenting community exposure to
ensure the protection of the surrounding community and documenting the exposure of on-site
workers (industrial hygiene). Since these two primary objectives may involve significant
differences in the sampling approach taken and in the type of equipment, as well as
differences in analytical methodology, the differences in costs can be substantial. The air
action levels (AALs) set for community exposure are normally much lower than equivalent
AALs for on-site workers, since on-site workers can use personal protective equipment.
Therefore, the evaluation of community exposure generally requires more sensitive
monitoring and analytical methods, thus increasing the costs of this type of monitoring.
The number and type of target analytes selected will influence the types of
analytical methods used and the detection limits that must be achieved; therefore, they may
have a significant impact on program costs. Depending on the analyte and associated
analytical method, analytical costs may run from as little as $25 for the determination of lead
on a high-volume filter to over $2000 per PUF sample for dioxins and furans. Savings in
analytical and data management costs can be achieved by selecting an appropriate subset of
the compounds present at the site as target analytes, instead of monitoring for an extensive
list of compounds.
The frequency of sample collection will have a significant effect on program
costs. For long-term programs, these costs may easily out-weigh all other monitoring costs,
6-1
-------
including capital equipment and operation costs. Depending on the estimated duration of the
program, it may be more cost-effective to use automated real-time monitoring or to set-up an
on-site laboratory than to use a more traditional approach of sending discrete samples to an
off-site analytical laboratory. Data turnaround and laboratory responsiveness should also be
factors in such a decision.
The duration of the monitoring program may influence the selection or
implementation of sampling and analytical methods. For example, a more labor-intensive
sampling approach might be considered for a three-week program than for a two-year
program. In general, the longer the program the more cost-effective automated real-time
monitoring becomes.
The cost estimates given in this section are based on the assumption that all
capital equipment for a given application would be acquired for the program, regardless of
the sampling duration. Although some ambient equipment can be leased (especially portable
real-time monitors), many monitors are not readily available or, if they are, they have short
recovery costs, such as 3-6 months.
Tables 6-1 through 6-3 present the estimated costs of an AAM program for
volatile, semi-volatile, and inorganic compounds. Whenever possible, costs are provided on
a per-unit or per-sample basis, both for equipment and analytical work. Other expenses,
such as labor requirements for network operation and data management and reporting are
given as estimated number of hours. The unit cost for labor and the actual labor hours
themselves may vary significantly, depending on the level of personnel involved and the
charge rates of the individuals or organizations actually performing the work. Therefore,
these estimates are, at best, general guidelines.
Program costs will of course vary considerably depending on the area of the
country, the availability of equipment manufacturers and suppliers, analytical laboratories and
contractors. These estimates should only be used to try to estimate "ballpark" costs that may
be associated with the start-up and execution of an ambient monitoring program. Of course,
6-2
-------
RPMs/OSCs or their designates should get detailed price quotes to determine actual program
costs before initiating or committing to an ambient monitoring program.
Site preparation costs also can vary considerably from site to site. These costs
will depend on the distances involved and the complexity of providing electrical service to
the monitoring location, on whether, and to what extent, site security needs to be provided
for each monitoring location, and on what other types of preparation the site needs.
Normally, the acquisition of electrical power will be the most costly item associated with site
preparation; therefore, if utility service is readily available, site preparation costs should be
in the low range of the estimates given.
The costs of real-time analyzers can vary over more than an order of
magnitude. The typical costs of selected categories of real-time monitoring equipment are
given in Table 6-4.
6-3
-------
Table 6-1
Estimated Costs for Implementing a VOC Air Monitoring Program
Cost Type
Capital Cost
Start-up Costs
Operational Costs
Data Management
and Reporting
Cost Elements
SJnit Costs ($)
Option 1 - Time-integrated whole-air canister sampling
Canister samplers
6-liter SUMMAฎ Canisters
Packing crates for shipping canisters
4000-12,000
500-800
100-300
Option 2 - Time-integrated sorbent tube sampling
Sorbent tube samplers
Sorbent tubes (per box)
500-10,000
50-250
Option 3 - Automated fixed-location continuous analyzers
Analytical equipment
Climate controlled shelters
Spare parts (per location/station)
2,000-150,000
8,000-15,000
2,000-5,000
Option 4 - Remote sensing systems (FI1R/UV-DOAS)
Analytical Equipment
Climate Controlled Shelter
Develop Monitoring Plan
Equipment set-up/installation - includes utilities,
site pad, manpower, etc. (per site)
Operator Training
Option 1 - SUMMAฎ canister analysis
Option 2 - Sorbent tube analysis
Option 3 - Calibration supplies/expendables
Quarterly field QA/QC audits (options 1, 2, & 3)
Laboratory audit (options 1 & 2)
Data validation (per site/month)
Database processing and maintenance (per
site/month)
Data interpretation and reporting (per site/month)
> 100,000
8,000-15,000
200-400 hours
2,000-15,000
80-160 hours
350-600
80-200
3,000-5,000
4,000-5,000
1,500-2,500
20-40 hours
20-40 hours
40-80 hours
6-4
-------
Table 6-2
Estimated Costs for Implementing a SVOC Air Monitoring Program
, Cbstl^pe ;
Capital Costs
Start-up Costs
Operational Costs
Data Management
and Reporting
f* \ Cost Elements
General Metal Works, PS-1 high-volume sampler
PS-1 calibration kit
Spare parts (per sampler)
Glass Sampling Cartridges (need approximately
6/sampler)
Monitoring Plan Development
Equipment set-up/installation - includes utilities,
site preparation (if required), and manpower (per
site)
Operator Training
Sampling media (including PUFs, sorbents, and
filters) per cartridge includes preparation
Analysis Costs (PCBs by GC/ECD)
Analysis Costs (PCBs by GC/MS)
Analysis costs (PCDDs/PCDFs by HRGC/HRMS)
Analysis costs (PCDDs/PCDFs by medium
resolution GC/MS)
Analysis costs (organochloride pesticides by BCD)
Analysis costs (organochloride pesticides by
GC/MS)
Analysis Costs (PAHs by HPLC)
Analysis Costs (PAHs by GC/MS)
Quarterly field QA/QC audit
Quarterly laboratory audit
Data validation (per site)
Database processing and maintenance (per
site/month)
Data interpretation and reporting (per site/month)
Unit Casts ($)
2000-2500
700-800
150-250
75-100
200-400 hours
1,000-5,000
40-80 hours
100-250
150-250
250-500
1,800-2,400
800-1,00
150-250
250-500
150-250
250-500
4,000-5,000
1,500-2,500
20-40 hours
20-40 hours
40-80 hours
6-5
-------
Table 6-3
Estimated Costs for Implementing an Inorganic Compound
Air Monitoring Program
Costl^ype
Capital Costs
Start-up Costs
Operational Costs
Data Management
and Reporting
Cost Elements
High-volume air sampler (TSP)
High-volume PMj0 air sampler
Spare parts (per sampler)
Low/medium-volume air samplers
Hardware for impinger sampling (CN~)
Monitoring Plan Development
Equipment set-up/installation - includes utilities,
site preparation (if required), and manpower (per
site)
Operator Training
Sampling media - quartz or glass fiber filters
Filter preparation/weighing
Filter digestion/analysis preparation
Analysis Costs - ICP-AES analysis - depending on
number of elements per scan
Analysis Costs - AAS - per element
Analysis costs - GFAAS - per element
Analysis costs cyanide
Quarterly field QA/QC audit
Quarterly laboratory audit
Data validation (per site)
Database processing and maintenance (per
site/month)
Data interpretation and reporting (per site/month)
Unit Costs ($)
1,800-2,500
4,000-4,500
150-250
2,000-4,000
500-1000
200-400 hours
1,000-5,000
40-80 hours
1-5
0.25-0.50 hours
20-40
45-250
20-40
20-40
40-100
4,000-5,000
1,500-2,500
20-40 hours
20-40 hours
40-80 hours
6-6
-------
Table 6-4.
Summary of Information for Selected Classes of Real-Time Instruments
5 Measurement System
Electrochemical
Total Hydrocarbon
Flame lonization Detector
Photoionization Detector
Thermal Detector
Solid State
Colorimetric
Solid
Paper Tape
Liquid
Spectrophotometric
Nondispersive Infrared
Optical Remote Systems
Gas Chromatograph
Gas Chromatograph/Mass Spectrometer
Particulate
Optical
Radiometric
Gases Measured
T, C, O2, THC, H2S, CO
THC, VOC, SVOC
VOC, SVOC
THC, H2
THC, T, C
VOC, SVOC, THC, T, C
02, T, C
T, Formaldehyde
VOC, SVOC, T, HC
VOC, SVOC, THC, T, C
VOC, SVOC, THC, T, C
VOC, SVOC, THC, T, C
TSP
PM10
Topical Cost
$1,500
$4,000 - $8,000
$5,000
$1,500
$2,000
$400
$5,000 - $10,000
$6,000
$7,500
>$100,000
$14,000
> $75, 000
$8,000
$14,000
KEY:
C = Combustibles SVOC
CO = Carbon Monoxide T
HC = Hydrocarbons THC
H2S = Hydrogen Sulfide TSP
O2 = Oxygen VOC
PM10 = Particles < 10 microns diameter
= Semi-Volatile Organic Carbon
= Toxic Compounds
= Total Hydrocarbons
= Total Suspended Particulates
= Volatile Organic Compounds
6-7
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SECTION 7
REFERENCES
1. Eklund, B. Procedures for Conducting Air Pathway Analyses for Superfund
Activities, Interim Final Document: Volume 1 - Overview of Air Pathway
Assessments for Superfund Sites. EPA-450/1-89-00la. February 1993.
2. Schmidt, C., et al. Procedures for Conducting Air Pathway Analyses for
Superfund Activities, Interim Final Document: Volume 2 - Estimation of
Baseline Air Emissions at Superfund Sites (Revised). EPA-450/l-89-002a
(NTIS PB90-270588). August 1990.
3. Eklund, B., et al. Procedures for Conducting Air Pathway Analyses for
Superfund Activities, Interim Final Document: Volume 3 - Estimation of Air
Emissions From Clean-up Activities at Superfund Sites. EPA-450/1-89-003
(NTIS PB89-180061/AS). January 1989.
4. Stoner, R., et al. Procedures for Conducting Air Pathway Analyses for
Superfund Activities, Interim Final Document: Volume 4 - Procedures for
Dispersion Modeling and Air Monitoring for Superfund Air Pathway Analyses.
EPA-450/1-89-004 (NTIS PB90-113382/AS). July 1989.
5. Draves, J. and B. Eklund. Applicability of Open Path Monitors for Superfund
Site Cleanup. EPA-451/R-92-001 (NTIS PB93-138154). May 1992.
6. Salmons, C., F. Smith, and M. Messner. Guidance on Applying the Data
Quality Objectives For Ambient Air Monitoring Around Superfund Sites
(Stages I & II). EPA-450/4-89-015 (NTIS PB90-204603/AS). August 1989.
7. Smith, F., C. Salmons, M. Messner, and R. Shores. Guidance on Applying
the Data Quality Objectives For Ambient Air Monitoring Around Superfund
Sites (Stage III). EPA-450/4-90-005 (NTIS PB90-20461 I/AS). March 1990.
8. U.S. EPA Removal Program Representative Sampling Guidance; Volume II -
Air. Draft Report.
9. U.S. EPA. Ambient Monitoring Guidelines for Prevention of Significant
Deterioration (PSD). EPA 450/4-97-007. May 1987.
10. U.S. EPA. Compendium of Methods for Determination of Toxic Organic
Compounds in Air. EPA/600/4-89-017. June 1988.
11. Ranum, D. and B. Eklund. Compilation of Information on Real-Time Air
Monitors For Use at Superfund Sites. Draft Report to Mark Hansen of EPA
Region VI. January 1993.
7-1
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12. NIOSH Manual of Analytical Methods, 3rd Edition, P.M. Eller, Editor. U.S.
Department of Health and Human Services, National Institute of Occupational
Safety and Health, Cincinnati, Ohio. February 1984.
13. Oliver, K.D., J.D. Pleil, and W.A. McClenny. "Sample Integrity of Trace
Level Volatile Organic Compounds in Ambient Air Stored in SUMMAฎ
Polished Canisters." Atmospheric Environment, Vol. 20. 1986.
14. Brymer, D.A., L.D. Ogle, W.L. Crow, M.J. Carlo, and L.A. Bendele.
"Storage Stability of Ambient Level Volatile Organics in Stainless Steel
Canisters." Proceedings of the 1988 APCA Conference.
15. Cox, R.D. "Sample Collection and Analytical Techniques for Volatile
Organics in Air." Proceedings of the 1988 APCA Conference.
16. Spellicy, R.L., W.L. Crow, J.A. Draves, W.H. Buchholtz, and W.H. Herget.
"Spectroscopic Remote Sensing: Addressing Requirements of the Clean Air
Act." Spectroscopy 6, 24 (1991).
17. Draves, J. (Radian). Personal communication. 1993.
18. Fairless, BJ. and J.L. Hudson. "Monitoring Ambient Air for Dioxins."
Proceedings of the 1988 EPA/APCA International Symposium on the
Measurement of Toxic and Related Air Pollutants.
19. 40 CFR, Part 50, Appendix B.
20. 40 CFR, Part 50, Appendix J.
21. U.S. EPA. Quality Assurance Handbook for Air Pollution Measurement
Systems; Volume I - Principles. EPA-600/9-76-005. March 1976.
22. U.S. EPA. Quality Assurance Handbook for Air Pollution Measurement
Systems; Volume II - Ambient Air Specific Methods. EPA-600/4-77-027a.
May 1977.
23. U.S. EPA. Quality Assurance Handbook for Air Pollution Measurement
Systems; Volume III - Stationary Source Specific Methods. EPA-600/4-77-
027b. August 1977.
24. U.S. EPA. Quality Assurance Handbook for Air Pollution Measurement
Systems; Volume IV - Meteorological Measurements. EPA-600/4-82-060.
February 1983.
25. U.S. EPA. Quality Assurance Handbook for Air Pollution Measurement
Systems; Volume V - Precipitation Measurement Systems. EPA-600/4-82-
042a. March 1983.
7-2
-------
26. U.S. EPA. Technical Assistance Document for Sampling and Analysis of
Toxic Organic Compounds in Ambient Air. EPA-600/4-83-027. June 1983.
27. U.S. EPA. Preparing Perfect Project Plans. EPA-600/9-89-087. October
1989.
28. U.S. EPA. Interim Guidelines and Specifications for Preparing Quality
Assurance Project Plans. EPA-600/4-83-004. December 1980.
29. Pritchett, T. Personal Communication to Bart Eklund of Radian Corporation.
February 1993.
30. Code of Federal Regulations. Quality Assurance Requirements for Prevention
of Significant Deterioration (PSD) Air Monitoring. Part 58, Appendix B.
7-3
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APPENDIX A
BIBLIOGRAPHY OF NTGS DOCUMENTS
-------
APPENDIX A
BIBLIOGRAPHY OF NTGS DOCUMENTS
ASF-1 Eklund, B. Procedures for Conducting Air Pathway Analyses for Superfund
Activities, Interim Final Document: Volume 1 - Overview of Air Pathway
Assessments for Superfund Sites (Revised). EPA-450/l-89-001a. February
1993.
ASF-2 Schmidt, C., et al. Procedures for Conducting Air Pathway Analyses for
Superfund Activities, Interim Final Document: Volume 2 - Estimation of
Baseline Air Emissions at Superfund Sites (Revised). EPA-450/l-89-002a
(NTIS PB90-270588). August 1990.
ASF-3 Eklund, B., et al. Procedures for Conducting Air Pathway Analyses for
Superfund Activities, Interim Final Document: Volume 3 - Estimation of Air
Emissions From Clean-up Activities at Superfund Sites. EPA-450/1-89-003
(NTIS PB89-180061/AS). January 1989.
ASF-4 Hendler, A., et al. Procedures for Conducting Air Pathway Analyses for
Superfund Activities, Interim Final Document: Volume 4 - Guidance for
Ambient Air Monitoring at Superfund Sites. April 1993.
ASF-5 U.S. EPA. Procedures for Conducting Air Pathway Assessments for Superfund
Sites, Interim Final Document: Volume 5 - Dispersion Modeling. [Proposed
document].
ASF-6 TRC Environmental Consultants. A Workbook of Screening Techniques For
Assessing Impacts of Toxic Air Pollutants. EPA-450/4-88-009 (NTIS PB89-
134340). September 1988.
ASF-7 Salmons, C., F. Smith, and M. Messner. Guidance on Applying the Data
Quality Objectives For Ambient Air Monitoring Around Superfund Sites (Stages
I & II). EPA-450/4-89-015 (NTIS PB90-204603/AS). August 1989.
ASF-8 Pacific Environmental Services. Soil Vapor Extraction VOC Control
Technology Assessment. EPA-450/4-89-017 (NTIS PB90-216995). September
1989.
ASF-9 TRC Environmental Consultants. Review and Evaluation of Area Source
Dispersion Algorithms for Emission Sources at Superfund Sites. EPA-450/4-
89-020 (NTIS PB90-142753). November 1989.
ASF-10 Letkeman, J. Superfund Air Pathway Analysis Review Criteria Checklists.
EPA-450/1-90-001 (NTIS PB90-1825447AS). January 1990.
ASF-11 Smith, F., C. Salmons, M. Messner, and R. Shores. Guidance on Applying
the Data Quality Objectives For Ambient Air Monitoring Around Superfund
Sites (Stage III). EPA-450/4-90-005 (NTIS PB90-20461 I/AS). March 1990.
ASF-12 Saunders, G. Comparisons of Air Stripper Simulations and Field Performance
Data. EPA-450/1-90-002 (NTIS PB90-207317). March 1990.
-------
ASF-13 Damle, A.S., and T.N. Rogers. Air/Superfund National Technical Guidance
Study Series: Air Stripper Design Manual. EPA-450/1-90-003 (NTIS PB91-
125997). May 1990.
ASF-14 Saunders, G. Development of Example Procedures for Evaluating the Air
Impacts of Soil Excavation Associated with Superfimd Remedial Actions. EPA-
450/4-90-014 (NTIS PB90-255662/AS). July 1990.
ASF-15 Paul, R. Contingency Plans at Superfund Sites Using Air Monitoring. EPA-
450/1-90-005 (NTIS PB91-102129). September 1990.
ASF-16 Stroupe, K., S. Boone, and C. Thames. User's Guide to TSCREEN - A Model
For Screening Toxic Air Pollutant Concentrations. EPA-450/4-90-013 (NTIS
PB91-141820). December 1990.
ASF-17 Winges, K.D.. User's Guide for the Fugitive Dust Model (FDM)(Revised),
User's Instructions. EPA-910/9-88-202R (NTIS PB90-215203, PB90-502410).
January 1991.
ASF-18 Thompson, P., A. Ingles, and B. Eklund. Emission Factors For Superfund
Remediation Technologies. EPA-450/1-91-001 (NTIS PB91-190-975), March
1991.
ASF-19 Eklund, B., C. Petrinec, D. Ranum, and L. Hewlett. Database of Emission
Rate Measurement Projects -Draft Technical Note. EPA-450/1-91-003 (NTIS
PB91-222059). June 1991.
ASF-20 Eklund, B., S. Smith, and M. Hunt. Estimation of Air Impacts For Air
Stripping of Contaminated Water. EPA-450/1-91-002 (NTIS PB91-211888),
May 1991 (Revised August 1991).
ASF-21 Mann, C. and J. Carroll. Guideline For Predictive Baseline Emissions
Estimation Procedures For Superfund Sites. EPA-450/1-92-002 (NTIS PB92-
171909). January 1992.
ASF-22 Eklund, B., S. Smith, P. Thompson, and A. Malik. Estimation of Air Impacts
For Soil Vapor Extraction (SVE) Systems. EPA-450/1-92-001 (NTIS PB92-
143676/AS), January 1992.
ASF-23 Carroll, J. Screening Procedures For Estimating the Air Impacts of
Incineration at Superfund Sites. EPA-450/1-92-003 (NTIS PB92-171917).
February 1992.
ASF-24 Eklund, B., S. Smith, and A. Hendler. Estimation of Air Impacts For the
Excavation of Contaminated Soil. EPA-450/1-92-004 (NTIS PB92-171925),
March 1992.
ASF-25 Draves, J. and B. Eklund. Applicability of Open Path Monitors for Superfund
Site Cleanup. EPA-451/R-92-001 (NTIS PB93-138154). May 1992.
ASF-26 U.S. EPA. Assessing Potential Air Impacts for Superfund Sites. EPA-451/R-
92-002. September 1992.
-------
ASF-27 Hueske, K., B. Eklund, and J. Barnett. Evaluation of Short-Term Air Action
Levels for Superfund Sites, (in press). April 1993.
ASF-28 Ranum, D. and B. Eklund. Compilation of Information on Real-Time Air
Monitors for Use at Superfund Sites, (in press). April 1993.
ASF-29 U.S. EPA. Air Emissions From Area Sources: Estimating Soil and Soil-Gas
Sample Number Requirements. EPA-451/R-93-002. March 1993.
ASF-30 Eklund, B. and C. Albert. Models For Estimating Air Emission Rates From
Superfund Remedial Actions. EPA-451/R-93-001. March 1993.
ASF-31 U.S. EPA. Contingency Analysis Modeling for Superfund Sites and Other
Sources. EPA-454/R-93-001. 1993.
ASF-32 Eklund, B., C. Thompson, and S. Mischler. Estimation of Air Impacts From
Area Sources of Paniculate Matter Emissions at Superfund Sites, (in press).
April 1993.
ASF-33 Dulaney, W., B. Eklund, C. Thompson, and S. Mischler. Estimation of Air
Impacts For Bioventing Systems Used at Superfund Sites, (in press). April
1993.
ASF-34 Eklund, B., C. Thompson, and S. Mischler. Estimation of Air Impacts For
Solidification and Stabilization Processes Used at Superfund Sites, (in press).
April 1993.
ASF-35 Dulaney, W., B. Eklund, C. Thompson, and S. Mischler. Estimation of Air
Impacts For Thermal Desorption Systems Used at Superfund Sites, (in press).
April 1993.
Affiliated Reports
Eklund, B., et al. Control of Air Emissions From Superfund Sites. Final
Revised Report. EPA/625/R-92-012. U.S. EPA, Center for Environmental
Research Information. November 1992.
-------
APPENDIX B
USEFUL CONTACTS AND TELEPHONE NUMBERS
-------
APPENDIX B
USEFUL CONTACTS AND TELEPHONE NUMBERS
1. EPA Regional Offices
Each EPA regional office has the following staff positions:
Air/Superfund Coordinator;
ARARs Coordinator; and
Air Toxics Coordinator.
The Air/Superfund coordinator is the best single point of contact for air issues related
to Superfund Sites. The individuals in the staff positions listed above can be reached through
the office switchboards at the following numbers:
l?;;;:RegWu:f:.
I
n
m
IV
V
VI
vn
vm
IX
X
".'$'.: iilxxaUon
Boston
New York
Philadelphia
Atlanta
Chicago
Dallas
Kansas City
Denver
San Francisco
Seattle
Telephone Number
(617) 565-3420
(212) 264-2657*
(215) 597-9800
(404) 347-3004
(312) 353-2000
(214) 655-6444
(913) 551-7000
(303) 293-1603
(415) 744-1305
(206) 442-1200
*Air Programs Branch x-2517
2. Air/Superfund Program Contact
The primary contact for the Air/Superfund program is Mr. Joseph Padgett of EPA's
Office of Air Quality Planning and Standards at (919) 541-5589.
3. Document Ordering Information
Documents can be obtained through the National Technical Information Service
(NTTS) at (703) 487-4650. Information of Air/Superfund reports that are not yet in the NTIS
system can be obtained from Environmental Quality Management at (919) 489-5299.
-------
Other sources of documents include:
EPA's Control Technology Center (CTC) at (919) 541-0800;
EPA's Center for Environmental Research Information (CERI) at (513) 569-
7562; and
U.S. Government Printing Office (USGPO) at (202) 783-3238.
4. Other Useful Contacts
Air and Waste Management Associates (412) 232-3444.
5. Hotlines
OAQPS TIN
Modem #
(919) 541-5742
The OAQPS TTN consists of the following:
:! Bulletin | Board ^t
AMTIC
APTI
CHIEF
CTC
EMTIC
OAQPS
SCRAM
!;.,::% Contact- .. ; ='
JoeElkins
Betty Abramson
Michael Hamlin
Joe Steigerwald
Dan Bivins
Herschel Rorex
Russ Lee
; Phone^1SEtimbeฃ
(919) 541-5653
(919) 541-2371
(919) 541-5232
(919) 541-2736
(919) 541-5244
(919) 541-5637
(919) 541-5638
AIRS Database
BLIS Database
(RACT/BACT/LAER)
NATICH Database
TOXNET
IRIS
Andrea Kelsey
Joe Steigerwald
Vasu Kilaru
Information
User Support
(919) 541-5549
(919) 541-2736
(919) 541-0850
(301) 496-6531
(513) 569-7254
-------
APPENDIX C
LIST OF VENDORS FOR ANALYTICAL AND SAMPLING EQUIPMENT
-------
Electrochemical Systems
k ' V* A
^v...-,, ^ ;Yeaaor
AIM USA
AIM USA
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Biosystems, Inc.
CEA Instruments Inc.
CEA Instruments Inc.
Capital Controls Co. Inc.
Gas Tech Inc.
Gas Tech Inc.
Gas Tech Inc.
Gas Tech Inc.
Industrial Scientific Corp.
Industrial Scientific Corp.
Industrial Scientific Corp.
Industrial Scientific Corp.
International Sensor Tech
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Metrosonics Inc.
Sensidyne Inc.
Instrument
Model 1100
Model 2000
Sentinel 4
TLV Sniffer
Model 505
Gas Pointer H
Sentinel 44
Sniffer 302
Sniffer 303
Cannonball 2
TG-BA
TG-KA
Multipoint Gas Detector 1660
GX-86
GX-91
HS-91
HS-91
HS560
CL266
MX 251
TMX410
Remote Link System III
Model MPU-16
Model MPU-44
Gas Pro SGM-1000
MPU-220 (Pump)
MPU-220 (Remote)
PM-7000
SS-2000
Gases Measured Illlyl
THC
Yes
Yes
Yes
Toxtes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Combustibles
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Abbreviations:
THC =
02
Total Hydrocarbon
Oxygen
-------
Total Hydrocarbon Systems: Flame lonization Dectors
% s ; Vendor
CSI
CSI
Eagle Monitoring
Eagle Monitoring
Eagle Monitoring
Eagle Monitoring
Foxboro Company
Foxboro Company
GOW-MAC Instrument Company
GOW-MAC Instrument Company
GOW-MAC Instrument Company
GOW-MAC Instrument Company
Heath Consultants
Heath Consultants
Heath Consultants
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Sensidyne Inc.
Thermo Environmental
Thermo Environmental
<
Instrument
HC 5002C
HC5002C
EM7000
EM700
EM7000
EM700
OVA-108
OVA-88
Model 23-500
Model 23-500
23500 TH Analyzer
23500 TH Analyzer
DP-IH
DP-EM
PF-II
Model 10 ISA
Model 1015H
Gas Corder - FID
Model 1015H
Model 1015A
JUM 109A
JUM - VE7
JUM 3-100
JUM 3-100
JUM 3-300
JUM 5-100
JUM - VE7
JUM 5-100
JUM 3-300
JUM 109A
400A
404A
402
404A
400A
402
Portable FID
Model 51
Model 51
Gases Measured
'VOC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
5-VOC
Yes
Yes
Yes
Yes
Yes
Yes
THC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
,n-CH4 '
Yes
Yes
Abbreviations:
VOC = Volatile Organic Compounds
S-VOC = Semi-Volatile Organic Compounds
THC = Total Hydrocarbons
n-CH4 = Non-Methane Hydrocarbons
-------
Total Hydrocarbon Systems: Photoionization Detectors
- Vendor
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
Photovac Inc.
Sentex Systems
Thermo Environmental
Thermo Environmental
Thermo Environmental
Thermo Environmental
Instrument
DL-101
HNU 201
HNU 201-250
HNU 201
HW-101
PI-101
HNU 201-250
IS-101
Model 1015C
R-Photon PID
Model 1015C
Gas Corder - PID
Microtip
Scentogun
Model 52
Model 580S
Model 52
Model 580 B
Gases Measured
VOC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
S-VOC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
THC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
H-CH4
Yes
Yes
Yes
Abbreviations:
VOC = Volatile Organic Compounds
S-VOC = Semi-Volatile Organic Compounds
THC = Total Hydrocarbons
-------
Total Hydrocarbon Systems: Others
*- ' Vendor
AIM USA
Bacharach Inc.
International Sensor Tech.
Matheson Gas Products
Matheson Gas Products
%
instrument
Model 1200
TLV Sniffer
Remote Link System III
Model 80SA
Custom Gas Del. Sys.
Detector
TD
EC, CB
EC, SS
SS, TC, Plat
SS
VOC
Yes
Yes
S-VOC
Yes
Yes
THJCJ:
Yes
Yes
Yes
Yes
Yes
leasureid ;-.:
*&&8&tง
Yes
Yes
Yes
!.''!. t .: :': : V- '!-!
Combustibles
Yes
Yes
Yes
Abbreviations:
VOC
S-VOC
THC
TD
EC
SS
TC
Plat
Volatile Organic Compounds
Semi-Volatile Organic Compounds
Total Hydrocarbons
Tin Dioxide
Electrochemical
Solid State
Thermal Conductivity
Platinum
-------
Spectrophotometric Systems
^ A . y.\ : :: f
'-.' -^, , ^faSof
CEA Instruments Inc.
MSA Instrument Division
Milton Roy
Rosemount Analytical Inc.
Foxboro Company
Foxboro Company
ABB Environmental
ABB Environmental
AIM USA
Anarad Inc.
MDA Scientific Inc.
MIDAC Corporation
Mattson Instruments Inc.
Nicolet Instrument Corp.
Bruel & Kjaer
Instrument
RI-411A
LIRA-3000
Model 3300A
880A
MIRAN203
MIRAN 1B-X
ER130
ER110
0PM
AR9000
FTIR Remote
Sensor
FTIR
REA-FTIR
FTIR 0PM
Type 1302
Detector
NDIR
NDIR
NDIR
NDIR
IR
IR
UV
UV
GFC
FTIR
FTIR
FTIR
FTIR
FTIR
IPA
Gases Measured
VOC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
s-yoc
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Tes
THC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Toxics
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Combustibles
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Others
Yes
Yes
Abbreviations:
VOC
S-VOC
THC
CO2
NDIR
IR
UV
GFC
FTIR
IPA
Volatile Organic Compounds
Semi-Volatile Organic Compounds
Total Hydrocarbon
Carbon Dioxide
Non-dispersive Infrared
Infrared
Ultraviolet
Gas Filter Correlation
Fourier-Transform Infrared
Infrared Photoacoustic Absorption
-------
Colorimetric Systems
Vendo?
CEA Instruments Inc.
MDA Scientific Inc.
MDA Scientific Inc.
MSA Instrument Division
Matheson Gas Products
National Draeger Inc.
Sensidyne Inc.
Instrument ..
TGM-555
Portable 7100
TLD-1
Detector Tubes
Matheson-Kitagawa
Detector Tubes
Detector Tubes
Detector
Liquid
Tape
Tape
Solid
Solid
Solid
Solid
Gases Measured
'VOC
Yes
Yes
Yes
Yes
S-VOC
Yes
Yes
Yes
Yes
THC
Yes
Yes
Yes
Toxics
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Combustibles
Yes
Yes
Yes
Yes
Yes
Others
Yes
Yes
Abbreviations:
VOC = Volatile Organic Compounds
S-VOC = Semi-Volatile Organic Compounds
THC = Total Hydrocarbon
-------
Gas Chromatograph/Mass Spectrograph Systems
^Waiter
CMS Research Corporation
Foxboro Company
HNU Systems Inc.
HNU Systems Inc.
MSA Instrument Division
MSA Instrument Division
MTI Analytical Instruments
MTI Analytical Instruments
MTI Analytical Instruments
Microsensor Systems
Microsensor Systems
Microsensor Systems
Microsensor Systems
Photovac Inc.
Photovac Inc.
Photovac Inc.
SRI Instruments Inc.
Sentex Systems Inc.
ABB Process Analytics
Extreal Corporation
ELI Eco-Logic
Viking Instruments
Instrument
2000 Minicams Sys
OVA-128
HNU 301-DP
HNU Model 311 GC
Model 8550
Model 1030A
Quad 400 gas analyzer
P 200 Microgas Anlyzr.
M200 Microgas GC
MSI-301A
MSI-301E
MSI-301B
MSI-301
10-S Plus
10-S Plus
Snapshot
Model 8610 GC
Scentograph
EnviroSpec 3000
Questor II Process MS
Sims 500
2400-700
Detector(s)
FID.PID.FP
FID
FID.PID.UV.ECD
PID.UV.ECD
FID,PID,TCD,HID,ECD
FID
SS
SS
SS
TCD
TCD
TCD
TCD
PID
PID
PID
FID,PID,FP,ECD,ELCD
PID.TCD.AID.ECD
MS
MS
MS
MS
Gases Measured
VOC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
s-voc
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
THC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Toxics
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Combust2>ks
Yes
Yes
Yes
Yes
Yes
Yes
Abbreviations:
VOC
S-VOC
THC
FID
PID
FP
UV
ECD
TCD
HID
SS
ELCD
AID
MS
Volatile Organic Compounds
Semi-Volatile Organic Compounds
Total Hydrocarbons
Flame lonization Detector
Photoionization Detector
Flame Photometric
Ultraviolet
Electron Capture Detector
Thermal Conductivity Detector
Helium lonization Detector
Solid State
Electroytic Conductivity Detector
Argon lonization Detector
Mass Spectrograph
-------
Particulate Samplers
Vendor
Anderson Samplers Inc.
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Dasibi Environmental Corp.
Mffilnc.
Mffilnc.
Mffilnc.
Mffilnc.
Mffilnc.
Mffilnc.
Sensidyne Inc.
Wedding & Associates
Instrument .:..
FH 61 1-N Beta
CI-4224
CI-4120
CI-7350
CI-4124
CI-4220
CI-7300
CI-7400
CI-4100
CI-4200
CI-7600
CI-7200
PM-10 Beta Gauge
FM-7400
PDM-3
RAS-2
RASSEx
RAM-1
RAM-5
LD-1
PM-10 Beta Gauge
' \- Detector
Radiation-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Radiation-based Particulate Monitor
Laser Fiber Detection
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Laser Light Scattering
Radiation-based Particulate Monitor
-------
APPENDIX D
CASE EXAMPLE
NOTE: This case example is a slightly modified version of a case example originally
published in "Guidance on Applying the Data Quality Objectives Process for
Ambient Air Monitoring Around Superfund Sites (Stage III)".
-------
D.I BACKGROUND
This hypothetical Superfund site, located on the outskirts of an urban area,
consists of approximately 180 acres. The fenced-in site property is mostly flat, covered by
weeds and brushes 1 to 2 meters in height. Also, there is a continuous row of both
deciduous and nondeciduous trees ranging from 18 to 23 meters in height, just inside the
boundary fence. Figure 1 is a scaled map of the site.
Site records indicate that approximately 20,000 drums containing waste from
local industries were buried here from 1959 until 1980. Most of the drums were buried in a
single layer at a depth of about 2 meters. The 3-acre area marked "A" in Figure 1
designates where the drums were buried. The drums contain mainly spent solvents
representing RCRA waste codes F001 through F006.
Some of the drums have leaked and contamination of soil and ground water is
possible. This potential problem led to a Remedial Investigation/Feasibility Study (RI/FS)
for the site. The remedial action selected following the RI/FS was to dig up the buried
drums, pack them into larger drums labeled as containing hazardous waste, and transport
them to a nearby hazardous waste facility. This remediation effort is expected to take 12
months of on-site activity based on an 8-hour, 5-day-a-week work schedule.
During the RI/FS, drums were disturbed and an unusual odor was detected at
the house identified as receptor Rl in Figure 1. A measurement made with a total VOC
instrument indicated that VOCs had been released into the air; therefore, monitoring will be
necessary to detect any subsequent releases to the ambient air which would pose a threat to
public health during remediation.
A State-operated meteorological monitoring station has been operating for a
number of years outside the fenceline of this site (see Figure 1). Its location adjacent to the
site is coincidental, but historical meteorological data such as wind speed, wind direction,
rainfall, and temperature will be useful in designing the monitoring network. In addition,
data from the nearest National Weather Service station could be used to provide
supplementary information.
D.2 WASTE CHARACTERIZATION
There are no compound-specific air monitoring data available for this site.
Therefore, to gain an understanding of which VOCs may be released to the atmosphere
during remediation, it was necessary to determine the composition of the buried waste. The
first step was to review the site records, which showed that the site contained waste codes
F001 through F006. A list of VOCs contained within each waste code was obtained from 40
CFR, Part 261 (subpart D, paragraph 261.31 of Table 1). Physical property data were then
used to rank the compounds according to their volatility (vapor pressure or Henry's Law
constant) and their toxicity (carcinogen or noncarcinogen) to select target compounds.
-------
Trees and brush,
combination of
spruce, pine, oak,
and maple, 18-23 m
Gravel road, fugitive
emissions control
with water spraying
Site Boundary
Open area
-1-2 m weeds,
brush, and grass.
Bush-hogged annually.
Designated route
for excavation work
and site visitors
agency air
monitoring
station
Elevation at 470 m;
grade is mostly flat ฑ 6m
0 60 120 180 240
1 cm = 60 m
ฎ Canister Sampling Site
N
Figure 1. Hypothetical Superfund Site with Location of Buried Drums.
-------
D.3 OVERVIEW OF AAM PROGRAM
The measurement system design consists of three monitoring strategies. First,
modeling data indicated that in the absence of open pools of liquid waste, the probability of
the residents at the receptor sites being exposed to VOC concentration levels of concern was
very small. Thus, a single screening strategy was designed to provide the RPM/OSC with
real-time information on total VOC concentrations near and downwind of the work site to
allow timely initiation of emission control procedures when necessary.
The second element selected for the monitoring system design was a refined
screening strategy. This strategy will be employed if the results from the screening work
show that a preset criterion has been exceeded. The reason for implementing the refined
screening strategy is to provide the RPM/OSC with real-time or near real-time concentrations
of the six indicator compounds near and downwind of the work site. Since the concentration
level of concern is different for each VOC, a knowledge of the individual VOC
concentrations provides the RPM/OSC with more information to assess the risk of not
initiating emission control actions than is available from the screening results. Also, this
refined screening strategy provides total VOC concentrations at the impacted receptor site in
real-time to allow for timely initiation of emission control actions and provide information on
short-term exposure levels.
When on-site measurements from the screening and/or refined screening
strategies exceed preset criteria (i.e., action levels), a third element of the monitoring
system, a quantitative assessment strategy will be employed to provide the RPM/OSC with 8-
hour average concentrations of individual VOCs at the receptor sites for that work day. The
monitoring methods that are selected should have detection levels equal to or lower than the
applicable action levels.
Procedures for selecting monitoring instrumentation for each of the three
monitoring strategies are discussed separately by strategy in the following subsections. The
selection process starts with a description of the performance and operational requirements of
the monitoring instrument. This is followed by an overview of the commercially available
instruments considered for this application. Finally, the instrument and associated apparatus
selected for this application are discussed.
D.4 INSTRUMENT SELECTION
Instrument Selection for Screening Strategy
The primary function of the monitoring instrument for the screening strategy is
to provide a continuous, real-time indication of VOC concentrations near and downwind of
the work site. There are several commercially available VOC monitors that provide real-
time data for total VOC concentrations.
The operational requirements and performance capabilities of an instrument for
this application are as follows:
Operate outside year-round.
-------
Operate continuously over an 8-hour work day without external
electrical power.
Be portable, easily carried by one person.
Respond to all six indicator compounds.
Have a detection limit of better than 1 ppm for isobutylene (the
calibration gas).
Be capable of recording the total VOC data over an 8-hour period.
Not respond to interferences common to Superfund sites including
methane, water, carbon dioxide, nitrogen, and oxygen.
Be capable of visual or audible alarms at preset total VOC
concentration levels.
There are a number of manufacturers marketing total VOC monitors. Each
manufacturer usually specializes in a monitor with one of two possible detectors: a flame
ionization detector (FID) and a photoionization detector (PID). Thus, the first decision in the
instrument selection process was to decide on the appropriate detection technique. The PID
responds to all six compounds with detection limits below the respective levels of concern
(0.1 of the OSHA Permissible Exposure Limit). The FID does not respond to carbon
disulfide. Also, a total VOC monitor equipped with a PID does not require a source of
hydrogen gas as does a monitor equipped with an FID. The FID hydrogen-burning system
requires more controls and a more complicated pneumatic system.
The instrument chosen for this task was a total VOC-PID monitor with the
following capabilities:
Designed to operate outside in the extremes of weather.
Designed to operate continuously throughout the 8-hour work day with
the use of an additional battery.
Is portable, easily carried by one person, and easy to operate and
maintain.
Responds to all six indicator compounds at concentration below the
respective levels of concern.
Shows a detection limit of 0.1 ppm for the calibration gas, isobutylene.
Incorporates advanced microprocessor technology for real-time digital
or graphic data assessment and built-in data logging capability for
storing data, including concentration with time and location.
-------
Does not respond to methane, water, carbon dioxide, nitrogen, and
oxygen.
Programmed to sound an alarm at predetermined total VOC
concentrations.
Instrument Selection for Refined Screening Strategy
The refined screening strategy provides the RPM/OSC with near real-time
concentrations of the six high-risk indicator compounds near the work site and total VOC
concentrations at the impacted receptor site. Also, the refined screening strategy will
provide information on the appropriateness of the six high-risk compounds selected as
indicators. This strategy will provide tentative identification of unknown compounds released
from the work site, serve to determine when to implement the quantitative assessment
strategy, and provide guidance on when to submit the quantitative assessment sample for
analysis by GC/MS to identify unknown compounds. This information is used to assess the
seriousness of the emissions from the work site.
The instrument for providing total VOC concentrations at the receptor is a
total VOC-PID. It was selected for the same reasons discussed in the screening strategy.
The operational requirements and performance capabilities of an instrument for
providing near real-time concentrations of at least the six indicator compounds near the work
site are as follows:
Operate outside year-round.
Operate continuously over an 8-hour work day without external
electrical power.
Be portable, easily carried by one person.
Respond to all six indicator compounds.
Have a detection limit of better than 1 ppm for benzene.
Be capable of recording the total VOC data over an 8-hour period.
Have a precision, expressed as a relative standard deviation, of 20% or
better for each of the six indicator compounds at their respective levels
of concern, and have a negligible bias.
There are a number of manufacturing marketing portable GCs which are
equipped with one or more detectors. The four available detection techniques are argon
ionization detector (AID), photoionization detector (PID), flame ionization detector (FID),
and electron capture detector (ECD). The PID and AID respond to all six indicator
compounds with detection limits below the respective levels of concern (0.1 PEL). The AID
and PID provide similar responses for four of the six compounds with the AID having
-------
superior sensitivity for the two remaining compounds. At least one of the six compounds
result in minimal or no response using the FID and ECD detection techniques.
The detection technique chosen for this application is the AID because of its
ability to respond to all six indicators. Once the detection technique was selected,
recommendations were solicited from individuals with experience using the portable GC-AID
in the field. One GC-AID monitor possessing all the required capabilities was reviewed and
selected for this application. The instrument chosen was a portable GC-AID monitor with
the following features:
Designed to operate outside in the extremes of weather.
Designed to operate on batteries and continue throughout the 8-hour
work day.
Is portable, easily carried by one person, and easy to operate and
maintain.
Responds to all six indicator compounds at concentrations below the
respective levels of concern.
Shows a detection limit of better than 0.1 ppm for benzene.
Incorporates advanced microprocessor technology for near real-time
data output. Data can be retrieved by either reviewing on a computer
screen or connecting the GC-AID to a printer. The computer program
provides peak identification of up to at least 9 peaks, calibration
information, and concentrations of the 9 peaks.
Instrument Selection for Quantitative Assessment Strategy
The purpose of the quantitative assessment strategy is to document the ambient
air 8-hour average concentrations that occurred at the receptors during the work day. Note
that the total VOC-PID monitor described in the refined screening strategy provides real-time
total VOC concentrations at the receptor site.
The operational requirements and performance capabilities of an instrument for
this application include the following:
It must collect a representative 8-hour sample year-round.
It must provide data of sufficient quality (precision and bias) for
meeting the DQOs.
It must provide concentration results within one week of sampling.
It must provide speciation of all VOC compounds identified in the
liquid waste.
-------
Sample collection can be conducted using either a sorbent or a stainless steel
canister. Summa canisters and adsorbent tubes have both been successfully used for ambient
air monitoring at Superfund sites. Both methods have their strengths, their applications, and
their problems. Experienced users of both methods believe that they are capable of
producing data of sufficient quality to satisfy the DQOs. For actual application, the selection
would probably be based on the personal preference of the user. For this illustration,
canister samplers serve as the selected method of collection 8-hour VOC samples.
To provide data of sufficient quality to satisfy the DQO, a laboratory GC is
required for analysis of the canister samples. A GC with one or more of three detectors or a
GC with mass spectrometry will provide the quality of data necessary. The three detectors
generally available are PID, FID, and ECD; many times, more than one detector would be
operated on the same GC (note the AID has lower detection limits but may not, at this time,
be available in most laboratories). The PID responds to all six indicator compounds with
detection limits below the respective levels of concern. For this application, the low
detection limits are important since most of the VOC concentrations will be below the levels
of concern. At least one of the six compounds provide minimal or no response using the
FID or ECD detection techniques.
Since both systems GC/MS and GC-PID with confirmation by FID will
reportably produce data of sufficient quality to satisfy the DQOs and have similar costs the
selection is based on convenience. Because of a local laboratory equipped with and
experienced in the use of GC-PID/FID, this becomes the method of choice for this
application.
The selected system will use evacuated canisters to collect an ambient air
sample and use GC-PID with confirmation by FID to analyze the ambient air sample. Ten
percent of the samples will be subjected to GC/MS for qualitative confirmation. The
primary criterion for subjecting a sample to analysis by GC/MS is an indication by the on-
site portable GC-AID monitor that unknown compounds were released from the work site
during that work day. These GC/MS analyses will be performed by a laboratory that does
not use a perma-pure drier in the GC/MS sampling line because of the potential sample
losses of methyl ethyl ketone and carbon disulfide. The canister will begin and end sampling
under a vacuum (not using a sample pump) to minimize the potential of contamination. The
canister analysis will be conducted by a laboratory with demonstrated experience.
Demonstrated experience was documented by participating successfully in the EPA's audit
cylinder repository program. Prior to initiating the remediation activities, the laboratory
chose to analyze the canisters will demonstrate capabilities for analysis of at least the six
indicator compounds.
The sampling system selected for this application will provide the following:
A representative 8-hour sample;
Detection limits of sufficient sensitivity;
A precision of 20% RSD (relative standard deviation) with no overall
bias to satisfy the DQOs; and
-------
Specification of all compounds expected to be emitted from the
Superfund site.
D.5 MONITORING SYSTEM DESIGN
One function of this monitoring system is to provide the RPM and/or on-site
coordinator (OSC) with data of sufficient quantity and quality to allow for timely initiation of
emission control actions. These emission control actions should preclude exposing the
subject population to VOC concentrations greater than the levels of concern. This function
of the monitoring system will be partially accomplished by a screening strategy that employs
a total VOC-PID monitor at the work site to provide real-time data on emissions from the
site. In addition, if the screening strategy results show that total VOC concentrations exceed
a preset level, a refined screening strategy is initiated. The refined screening strategy
employs two instruments, a portable GC-AID near the work site to provide near real-time
concentration values for the six high risk indicator compounds and a total VOC-PID at the
receptor site to provide real-time total VOC concentrations. This limited speciation by the
portable GC-AID will reveal the presence or absence of the high risk compounds. The
presence of one or more of these compounds at preset concentration levels will be reason to
alert the RPM/OSC to initiate emission control actions, and, under certain conditions, to shut
down the remediation activity. The total VOC concentrations measured at the receptor site
will also be used to alert the RPM/OSC if predetermined concentrations are exceeded.
Another important function of the monitoring system is to generate data
necessary to preclude the RPM/OSC from unnecessarily slowing or stopping the remediation.
This function is also fulfilled by using the refined screening strategy. As part of the refined
screening strategy, the portable GC-AID is deployed to provide compound-specific data on
the high risk compounds. For example, if the total VOC-PID monitor at the work site
indicates a VOC concentration of 100 ppm, the RPM/OSC may be inclined to stop the
remediation activity if, for example, the portable GC-AID indicates that the total 100 ppm is
benzene, which has a PEL of 1 ppm. Conversely, the RPM/OSC would not be as concerned
if the total 100 ppm was, for example, methyl ethyl ketone (which has a PEL of 200 ppm).
Thus, this function of the monitoring system could be very important in the overall efficiency
of the remediation program. Also, results from the portable GC-AID can be used to provide
tentative identification of unknown compounds by comparing the observed relative retention
time of an unknown peak against relative retention times that had been obtained for the more
volatile, non-indicator compounds. The other part of the refined screening strategy involves
deploying a total VOC-PID monitor at the nearest impacted receptor site. This total VOC-
PID monitor at the receptor site will be used to inform the RPM/OSC that VOCs emitted at
the work site are reaching the receptor site.
A third function of the monitoring system is to provide information of
sufficient quantity and quality to assure the RPM/OSC, decision maker, and residents at the
receptor sites that the DQOs were met. This function is fulfilled by the quantitative
assessment strategy consisting of an evacuated canister that collects an 8-hour sample at the
subject receptor site for subsequent analysis by laboratory GC-PID with FID confirmation.
The precision, bias, and speciation capabilities of this procedure indicate that the DQOs will
be satisfied for the compounds of interest for this Superfund site. Since real-time will not be
available, the action levels should be reasonably conservative. There is conflicting data on
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the stability of methyl ethyl ketone and carbon disulfide in canisters. For this illustration it
is assumed that they are stable. Recent evaluation tests indicate that at least methyl ethyl
ketone can be successfully collected in canisters.
A special characteristic of this site that has influenced the monitoring system
design is that the fenceline around the site is lined with a row of full-grown trees,
invalidating the customary procedure of monitoring at the fenceline. This factor, plus the
closeness of the receptor sites to the fenceline, means that the sample must be collected at or
adjacent to the receptor to be representative of the air at the receptor.
Based on the modeling data and to fulfill the three functions described above,
three different monitoring strategies are being employed for this project.
Screening at the work site for total VOC concentrations in real-time.
Refined screening at the work site for near real-time concentrations of
the six indicator compounds and at the receptor site for real-time
concentrations of total VOCs.
Quantitative assessment at the receptor site for integrated 8-hour
averages of individual VOCs.
These monitoring strategies will be used together to guide the on-site personnel in applying
emission control actions and to document off-site concentrations at the receptor sites.
Design for Screening Measurements
Screening is the least costly monitoring strategy, but provides the least amount
of information. It does provide real-time data, however, allowing for a quick response to a
problem should one occur. Screening is to be employed at the beginning of the project
and/or work day and will continue until emissions from the work site result in a measured
VOC concentration that exceeds a preset level. The monitoring system selected for screening
is a total VOC-PID monitor. This monitor will serve dual roles. It will provide health and
safety data and screening data for the potential off-site migration of VOCs emitted from the
work site.
For the screening strategy, when not in conflict with health and safety
monitoring, the total VOC-PID monitor will be positioned on a stable tripod 30 meters
downwind of the work site and operated for the 8-hour work day. The monitor will be
repositioned at least once an hour if necessary to remain in the plume center directly
downwind of the work site. An on-site meteorological station will be used to gauge the
direction of the emission plume from its source. In addition, wind socks will be located near
major emission sources. (As needed, or when operation in the refined screening level, the
total VOC-PID monitor can be used to evaluate upwind concentrations and/or to help the on-
site personnel locate the exact emission source at the work site.)
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Based on modeling data, the probability of experiencing VOC concentration
levels of concern at any of the receptor sites is very low. Thus, this simple screening
measurements may prove to be the only air monitoring required during the remediation
program.
Screening results are available in real-time and are used to alert the on-site
personnel to potential problems. Specifically, results from the total VOC-PID monitor based
on preset criteria are used to:
Alert the RPM/OSC that there is an emission source, allowing the
source to be located and controlled if necessary;
Alert the RPM/OSC to check the proper protective clothing is being
worn;
Direct the monitoring crew to initiate refined screening; and
Direct the RPM/OSC to initiate emission control actions.
Design for Refined Screening Measurements
Refined screening is employed when a potential problem is indicated by the
total VOC-PID response. Refined screening is more costly than screening, but it provides
some compound-specific information, allowing the RPM/OSC to better evaluate the
seriousness of the problem. The portable GC-AID monitor selected for refined screening can
be programmed to identify and quantify at least nine compounds. The nine programmed
compounds can be changed if unexpected compounds posing high risk to the resident
population are identified during the clean-up process. Initially, the portable GC-AID monitor
will be programmed to identify and quantify responses for the six indicator compounds. The
total VOC-PID monitor for this strategy is in addition to the one used in the screening
strategy. It provides the RPM/OSC real-time data on total VOC concentration at the
impacted receptor site.
Refined screening is conducted with the portable GC-AID monitor positioned
30 meters downwind of the work site. The instrument must be calibrated and ready for
operation at any time during the 8-hour work day. It should be capable of being placed on-
site and generating data within 15 minutes. The portable GC-AID monitor will be
repositioned as necessary, but at least once an hour (while refined screening is in effect) to
stay in the plume center-line, directly downwind of the work site. An alternative approach to
be considered is to set-up the portable GC-AID in the on-site laboratory and take syringe
samples in the field for analysis in the laboratory.
The total VOC-PID will be located at the receptor site with the highest
probability of being affected should a spill occur. This monitor will be used during the work
day and after work hours on evenings when meteorological conditions indicate that there
could be an atmospheric temperature inversion.
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Concentration values for up to nine compounds are provided by the portable
GC-AID approximately once every 10 minutes. These compound-specific data help the
RPM/OSC know when to take action and the proper action to take.
Results from the portable GC-AID monitor based on preset criteria are used
to:
Notify the monitoring crew to go to the quantitative assessment
strategy, or
Notify the RPM/OSC to initiate emission control actions.
Design for Quantitative Assessment Measurements
Quantitative assessment strategy provides more compound-specific information
than does refined screening. Results from the quantitative assessment strategy are directly
applicable to the receptor site. The monitoring system selected for this level of monitoring
includes the use of an evacuated canister to collect the sample and a laboratory GC-PID with
FID confirmation for analysis. Also, at least 10% of the canister samples analyzed will be
subjected to GC/MS for qualitative confirmation. Specifically, the downwind canister
sample(s) collected on days that the portable GC-AID results indicate that unknown
compounds were released from the work site will be subjected to GC/MS analysis to identify
the unknown compounds.
For quantitative assessment, one or two receptor areas identified as having the
greatest probability of being impacted (i.e., being downwind of the work site) will be
instrumented with an evacuated canister sampling system. Meteorological information will
be used to identify the site(s). In areas where two or more receptors are located, a sampling
site will be selected so as to be representative of all these clustered receptors Also, an
upwind or parallel site will be selected and instrumented. On a predetermined schedule a co-
located sampler will be placed at the receptor site most likely to be impacted as part of the
QA program. The samplers must be in place and operating over the 8-hour work day.
Results from the portable GC-AID and/or total VOC-PID, combined with meteorological
data, will be used to determine if the collected sample will be forwarded to the off-site
laboratory for analysis.
Results from analysis of quantitative assessment samples are not available until
about two days after sample collection. Thus, the data will be used to develop a data base
documenting VOC concentration levels experienced at one or more of the receptor sites for
various work-site situations. For example, values for the ratio of the concentrations of an
indicator compound at the work site and the receptor site for known meteorological and work
site conditions (for example, multiple accidental spills) will be calculated. This information
will assist the RPM/OSC in making decisions about the need for emission control actions
under similar future work site conditions.
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Results of quantitative assessment strategy based on preset criteria will be used
to:
Notify the RPM/OSC that remediation procedures must be changed to
reduce emissions if levels of concern are regularly approached or
frequently exceeded at one or more receptor sites.
Notify the RPM/OSC that certain receptor sites must be evacuated
before continuing remediation if the levels of concern are regularly
exceeded in spite of attempted emission control procedures.
Provide the RPM/OSC with accurate measures of VOC concentration
levels experienced at receptor sites.
D.6 CRITERIA FOR EMPLOYING A MONITORING STRATEGY
The criteria for moving from one strategy to another is based on measured
VOC concentrations. In the absence of VOC ambient air measurement data, the criteria are
purposely set to error on the side of safety. These criteria will be re-evaluated and changed
if necessary as monitoring data become available. The criteria are discussed for each
strategy in the following subsections.
The screening strategy is to be employed at the beginning of each work day,
unless experience has shown that the remedial activity will result in emission levels that
trigger the need for refined screening. The criterion for moving up to the refined screening
strategy is any time the total VOC response exceeds 5 ppm for 10 consecutive minutes. This
is also the safety criterion for changing from Level C to Level B dress for on-site workers.
Moving from the refined screening strategy back to the screening strategy is
accomplished by simply discontinuing the use of the portable GC-AID. The criterion for this
move is when the total VOC-PID response has been below 5 ppm for two consecutive hours
after the incident that triggered the need for refined screening.
The rationale for the criterion of 5 ppm VOC for 10 consecutive minutes (in
addition to it being the safety criterion) follows: benzene, identified as posing the highest
risk form the list of compounds in the buried waste, has a PEL of 1 ppm. If, for example,
the refined screening results showed the 5 ppm VOC measurement to be 5 ppm benzene,
then the RPM/OSC will be notified to initiate emission control actions. Likewise, if the 5
ppm VOC was shown to be 5 ppm methyl ethyl ketone, which has a PEL of 200 ppm, the
remediation activity could proceed unimpeded.
The refined screening strategy is employed whenever the total VOC-PID
response has exceeded 5 ppm for more than 10 consecutive minutes, or at the beginning of
the work day if experience indicates a high probability that initiation of remediation will
result in screening results greater than 5 ppm.
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The quantitative assessment strategy is implemented in the event that results
from either the on-site portable GC-AID or the total VOC-PID monitor located at the
receptor site exceed preset values. The quantitative assessment strategy is then initiated (that
is, one or both of the downwind canister samples (plus the upwind, co-located and trip blank
samples) is forwarded to the laboratory for analysis at the end of the 8-hour work day) if the
calculated Em is greater than 1 for 30 minutes or more during the work day.
A second criterion, independent of the portable GC-AID result, is based on
total VOC measurements at the receptor site. The quantitative assessment strategy is
initiated if the refined screening strategy results show total VOC concentrations greater than
0.5 ppm for 30 minutes or more during the work day.
These criteria are subjective; however, compound concentrations giving an
equivalent exposure value greater than 1 occurring 30 meters downwind of the work site may
result in measurable levels at the impacted receptor site(s). Also, a total VOC concentration
of 0.5 ppm, corrected for background levels, signal the need for application of emissions
control actions at the work site.
The reason for having two criteria, one based on total VOC and one on
compound-specific results, is that the total VOC concentration may represent compounds
other than the six indicator compounds. The quantitative assessment strategy would identify
and quantify all VOCs present at or above detection limit concentrations.at the receptor site.
Criteria for taking actions based on screening strategy results follow:
If the total VOC-PID response is 5 ppm or greater for 10 successive
minutes, alert the RPM/OSC that there is an emission source so that the
source may be located and controlled as necessary.
If the total VOC-PID response is 5 ppm or greater for 10 successive
minutes, alert the RPM/OSC to check that proper protective clothing is
being worn.
If the total VOC-PID response is 200 ppm or greater for 10 successive
minutes, alert the RPM/OSC that emissions must be reduced within the
next 30 minutes or halt the remediation activity. (This applies only if
the monitoring staff for some reason has been unable to initiate the
refined screening strategy in this time period.)
The rationale for the criterion of 5 ppm total VOC is that benzene could
account for the major portion of the VOC measurement. Benzene has a short-term exposure
limit (STEL) of 5 ppm; thus, the on-site workers would be alerted to wear the proper
protective clothing. Also, a potential 5 ppm concentration of benzene 30 meters downwind
of the work site may result in a concentration near the level of concern (100 ppb) at one of
the receptor sites.
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The rationale for the criterion of 200 ppm for 10 successive minutes is that on-
site VOC concentrations at this level will probably result in measurable VOC concentrations
off-site.
The compound-specific information provided by the portable GC-AID monitor
is used to guard against allowing one or more of the high risk compounds to reach the
receptor site at concentration levels near one tenth of their respective PELs.
There are two criteria for initiating emissions control actions based on refined
screening data. The two should be evaluated separately, that is action must be taken should
either one be exceeded. The criterion for emission control actions follows:
The RPM/OSC is notified that emissions must be reduced within 30
minutes or remediation will have to be halted if the portable GC-ATD
monitor response results in a calculated Em greater than 1 for 10
successive minutes.
The RPM/OSC is notified that emissions must be reduced within 30
minutes or remediation will have to be halted if the total VOC-PID
monitor at the receptor site shows a concentration of 0.5 ppm or
greater for 10 successive minutes.
The rationale for the criterion of ฃ, > 1 for 10 successive minutes is that one
or more of the six indicator compounds could be present at concentrations near their
respective PEL which could result in receptor site concentrations near the levels of concern.
A total VOC concentration of 0.5 ppm at the receptor site is one tenth of the work site
criterion of 5 ppm for moving from Level C to Level B protective clothing. This is the same
rationale used for establishing the level of concern at one tenth of the PEL.
Quantitative assessment results directly estimate the health risks experienced
by residents at the receptor sites. Thus, these results are used by the RPM/OSC to assess
when the remediation process being used needs to be changed so that emissions are reduced.
Criteria for taking action based on quantitative assessment strategy results
follow:
The RPM/OSC is notified that remediation procedures must be changed
to reduce emissions if any compound identified routinely approaches or
exceeds 0.1 PEL, or that the remediation activity must be halted.
The RPM/OSC is notified that a certain receptor site must be evacuated
during the 8-hour work day when meteorological information indicates
that it will be in the plume's path and if results have shown one or
more compounds to exceed 0.2 PEL under similar meteorological
conditions. Otherwise, the remediation activity must be halted.
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These above criteria of 0.1 PEL and 0.2 PEL are used here because they are
the concentration levels of concern (0.1 PEL) and the concentration level at which the
decision maker stated that the monitoring system should be such that the probability of a
false negative is no greater than 1 percent.
D.7 ESTIMATED TOTAL LABOR AND COST
In Stage I of the DQO, the following resources were made available for this
ambient air monitoring effort:
A mobile laboratory to be placed on-site for the duration of the clean-
up operation.
Equipment necessary for cleaning the SUMMAฎ canisters in the on-site
laboratory.
Two monitoring technicians to be dedicated to this air monitoring effort
(i.e., 2 FTEs).
The monitoring effort is estimated to require a total work force of 3 FTEs.
Thus, one FTE will be required in addition to the two provided by the ESD. It is important
to not over-commit the on-site workers because concentrated monitoring activities could
occur at any time and the monitoring staff needs to be prepared. The three monitoring
personnel will probably have to stagger their shifts in order to fully service the three
monitoring systems before and after the work day. That is, the two total VOC-PID monitors
and the portable GC-AID must be calibrated before and after each work day. Also the
canisters must be deployed and the samplers set to take a sample spanning the 8-hour work
day. Costs have been estimated for each monitoring strategy and are based on the
assumption that the refined screening and quantitative assessment strategies will be required
infrequently.
Individual costs estimates listed below are only for illustrating the process.
The individual item costs are believed to be reasonable but they do not represent actual
quotes from manufacturers or contractors nor is the listing presented as a comprehensive list.
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Project Planning
DQO Package
- Sampling and analysis plan
- Quality assurance project plan
- Summary work plan
Subtotal:
$75,000
$75,000
Manpower
One technician (1 FTE) (estimated at $2,500 per week for 52
weeks this includes per diem, overtime, etc.)
Subtotal:
$130,000
$130,000
Screening Strategy Costs
Purchase price of total VOC-PID monitor
Supplementary field kit
Supplementary battery
Replacement battery
Replacement lamp
Inlet filters (5)
Calibration standard
Subtotal:
$4,500
600
300
300
215
25
500
$ 6,440
Refined Screening Strategy Costs
Purchase price of portable GC-AID monitor
Spare parts and filters
Calibration standard and carrier gas for portable GC-AID
Purchase price of total VOC-PID monitor and needed supplies
Subtotal:
$ 20,500
525
3,100
6,440
$30,565
Quantitative Assessment Strategy Costs
Purchase price of canister sampler (4)
Purchase price of 34 canisters
Canister analysis by GC-PID/FID at $500 per sample (130)
Canister analysis by GC/MS at $1,000 each (5 assumed)
Subtotal:
$ 20,000
25,000
65,000
5,000
$115,000
GRAND TOTAL:
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-451/R-93-007
3. RECIPIENT'S ACCESSION NO.
4..TirLE AND SUBTITLE . ,.,ซ.., ซ
Air/Superfund National Technical Guidance Study
Series - Volume IV - Guidance for Ambient Air
Monitoring at Superfund Sites
5. REPORT DATE
May 1993
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
3501 Mo-Pac Boulevard
Austin, Texas 78159
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report presents the results of an EPA-sponsored study to develop guidance for
designing and conducting ambient air monitoring at Superfund sites. By law, all exposure
pathways - including the air pathway - must be evaluated for every Superfund site; therefore,
some level of ambient air monitoring usually is necessary at each site.
This document offers technical guidance for use by a diverse audience, including EPA Air
and Superfund Regional and Headquarters staff, State Air and Superfund staff, federal and state
remedial and removal contractors, and potentially responsible parties. This manual is written to
serve the needs of individuals with various levels of scientific training and experience in selecting
and using ambient air monitoring methods in support of air pathway assessments.
There is no universal approach to conducting an ambient air monitoring program that
would satisfy the needs of every air pathway assessment. Instead, each program should be
designed to match the specific program needs and available resources. A framework for
designing an effective ambient air monitoring is presented in the document. The framework
parallels earlier EPA guidance on applying the Data Quality Objectives Process for ambient air
monitoring around Superfund sites.
IT*
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b-IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Superfund
Air Monitoring
VS. DISTRIBUTION STATEMENT
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EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDI TION i s OBSOLETE
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