United States Office of Air Quality EPA454/R-01-003

Environmental Protection Planning and Standards February 2001

Agency Research Triangle Park, NC 27711

AIR

 Pilot City Air Toxics 

 Measurements Summary

This document is intended only for use by the participants in the FY2000 and FY2001 Ambient

Air Toxics Pilot Monitoring Program and does not constitute guidance which is generally

applicable to State and local agencies. Its purpose is to ensure consistency among Pilot

monitoring project measurements so that analyses of the resulting data can be evaluated based on

minimal variables.
Pilot City Air Toxics Monitoring Study

Table of Contents

Foreword .................................................................... 1

1.0 Background ............................................................... 2

2.0 Method Detection Limit (MDL) .............................................. 3

2.1 Volatile Organic Compound (VOC) HAPs ................................. 4

2.2 Carbonyl Compounds ................................................. 5

2.3 Metals and Compounds ............................................... 5

3.0 Uncertainty (Precision) ...................................................... 6

4.0 National Performance Audit Program (NPAP) - Bias .............................. 8

5.0 Stability and Hold Times ..................................................... 8

5.1 Volatile Organic Compound (VOC) HAPs ................................. 8

5.2 Carbonyl Compounds ................................................. 9

5.3 Metal Compounds .................................................... 9

6.0 Measurement Procedures ................................................... 9

6.1 Volatile Organic Compounds (VOCs ) .................................... 9

6.1.1 Humidification of VOC Canister Calibration Standards ............. 10

6.1.2 Canister Certification ......................................... 10

6.2 Carbonyl Analysis ................................................... 10

6.3 Metals Analysis .................................................... 12

6.3.1 Extractable versus Total Metals ................................ 12

7.0 Data Reporting ........................................................... 14

7.1 Lowest Calibration Level (LCL) ....................................... 14

8.0 Clarification of Terminology ................................................. 15

8.1 Detection Limits .................................................... 15

8.1.1 Method Detection Limit (MDL) ................................ 15

8.1.2 Limit of Detection (LOD) ..................................... 15

8.1.3 Detection Limit (DL) ......................................... 16

8.1.4 Instrument Detection Limit (IDL) ............................... 16

8.2 Quantitation Limits .................................................. 16

8.2.1 Minimum Level (ML) ........................................ 16
Pilot City Air Toxics Monitoring Study

8.2.2 Limit of Quantitation (LOQ) ................................... 17

8.2.3 Practical Quantitation Limit (PQL) .............................. 17

8.2.4 Minimum Reporting Level (MRL) .............................. 17
Pilot City Air Toxics Monitoring Study

Appendix A

Compendium Method TO-15A, “Determination of Volatile Organic Compounds in Air

Collected in Specially-prepared Canisters and Analyzed by Gas Chromatography/Mass

Spectrometry, GC/MS

Appendix B

Procedure for Humidification, Section 2.3.4.3.1 taken from the PAMS Technical Assistance

Document for the Sampling and Analysis of Ozone Precursors,

EPA/600-R-98/161

Appendix C

Compendium Method TO-11A, “Determination of Formaldehyde in Ambient Air Using

Adsorbent Cartridge Followed by High Performance Liquid Chromatography, HPLC“

Appendix D

DRAFT Guidance for Carbonyl Measurements at PAMS

Appendix E

“Methodology for Determining Carbonyl Compounds in Ambient Air”, Section 5 from the

PAMS Technical Assistance Document for the Sampling and Analysis of Ozone,

Precursors, EPA/600-R-98/161

Appendix F

Inorganic Compendium Method IO-3.5, “Determination of Metals in Ambient Particulate

Matter Using Inductively Coupled Plasma/Mass Spectrometry, ICP/MS”

Appendix G

Inorganic Compendium Method IO-3.1, “Selection, Preparation and Extraction of Filter

Material”

Appendix H

Appendix B to Part 136 - “Definition and Procedure for the Determination of the Method

Detection Limit”, Revision 1.11
Pilot City Air Toxics Monitoring Study

List of Tables 

Table 1. VOC Analysis via TO-15A GC/MS for Air Toxics Pilot Monitoring Programs ..... 9

Table 2. Carbonyl Analysis via TO-11A HPLC for Air Toxics Pilot Monitoring Program . . 11

Table 3. TSP Analysis via IO-3.5 ICP/MS for Air Toxics Pilot Monitoring Program ....... 13
Pilot City Air Toxics Monitoring Study

1

Foreword

In order to provide consistency in the data set generated by the Pilot Toxics Monitoring

network, a laboratory measurements work group was formed to discuss the procedures to be used for

measurements. This group of laboratory, State, local, Regional and EPA representatives had a series of

discussions to define critical details of the measurement procedures needed to provide data to meet the

needs of the NATA, the data users, and the national air toxics Pilot City monitoring program. The

purpose of this document is to outline the procedures that the laboratory work group have defined. The

document is to be used as a supplement to the EPA Compendium of Methods identified for use by the

Pilot City network. Specifically, Method TO-15A, “Determination of Volatile Organic Compounds in

Air Collected in Specially Prepared Canisters and Analyzed by Gas Chromatography/Mass

Spectrometry, GC/MS.”; TO-11A, “Determination of Formaldehyde in Ambient Air Using Adsorbent

Cartridge Followed by High Performance Liquid Chromatography, HPLC“; and IO-3.5,

“Determination of Metals in Ambient Particulate Matter Using Inductively Coupled Plasma/Mass

Spectrometry, ICP/MS”. 

Although the details of the procedures described below are not entirely consistent with the

Compendium of Methods, items called out in this document are specific to the data quality goals of the

Pilot monitoring program. This guideline is provided to assist states in implementation of the Pilot

monitoring network. This document is not policy and does not contain legally binding requirements, nor

is it regulation. It is intended only for use by the participants in the FY2000 and FY2001 Ambient Air

Toxics Pilot Monitoring Program and does not constitute guidance which is generally applicable to

State and local agencies. Its purpose is to ensure consistency among Pilot monitoring project

measurements so that analyses of the resulting data can be evaluated based on minimal variables. This

document is intended for use by those already familiar with the analysis of field samples for volatile

organic compounds (VOCs), carbonyl compounds and metals.

As this document is being issued, a Data Management work group is being convened to identify

and resolve issues related to reporting of data (e.g., concentration data reporting units, AIRS method

codes, etc.). Please refer to the reports of this group for clarification of data management issues.
Pilot City Air Toxics Monitoring Study

February 2001 2

1.0 Background

To address the concerns about the prevalence of air toxics emissions and to meet EPA’s

strategic goals, a national air toxics program has been designed to characterize, prioritize, and equitably

address the impacts of HAPs on the public health and environment. The national air toxics program

seeks to address air toxics problems through a combination of activities and authorities, including

regulatory approaches and voluntary partnerships. One of the key activities is the National Air Toxics

Assessment (NATA). NATA activities will help EPA identify areas of concern, characterize human

health and ecosystem risks and track progress of trends. 

As outlined in the air toxics monitoring “Concept Paper”, posted at

http://www.epa.gov/ttn/amtic/files/ambient/airtox/cncp-sab.pdf, the role of ambient monitoring to

support NATA activities includes:

• characterization of ambient concentrations and deposition in representative monitoring areas;

• provide data to support and evaluate dispersion and deposition models; and 

• establish trends and evaluate the effectiveness of HAP reduction strategies.

In addition, initial pilot monitoring together with data analysis of existing measurements will be needed to

provide information on spatial and temporal variability of ambient air toxics. This information will aid in

providing state and local air agencies important information about their particular network needs. The

pilot monitoring program will also provide very useful information to help the EPA design a long-term

national air toxics monitoring network.

In order to provide consistency in the data set generated by the Pilot City Program, a

laboratory work group was formed to discuss the details regarding procedures to be used for

measurements. This group of laboratory, State, local, Regional and EPA representatives met to define

critical details of the measurement procedures needed to provide data that will meet the needs of the

NATA, the data users, and the national air toxics monitoring program. The primary goal of the

laboratory work group was to develop consistent procedures for use by all cities participating in the

Pilot Study in order to maximize the data comparability. Consistency and comparability of data is very
Pilot City Air Toxics Monitoring Study

February 2001 3

important due to differences in data reporting procedures, method detection limit determination, and

other issues that may create an artificial bias in the data base as a result of the preponderance of values

not detected.

The purpose of this document is to outline the procedures that the laboratory measurements

work group have defined. The document is to be used as a supplement to the EPA Compendium of

Methods identified for use by the Pilot City network. Specifically, Method TO-15A, “Determination of

Volatile Organic Compounds in Air Collected in Specially Prepared Canisters and Analyzed by Gas

Chromatography/Mass Spectrometry, GC/MS.”; TO-11A, “Determination of Formaldehyde in

Ambient Air Using Adsorbent Cartridge Followed by High Performance Liquid Chromatography,

HPLC“; and IO-3.5, “Determination of Metals in Ambient Particulate Matter Using Inductively

Coupled Plasma/Mass Spectrometry, ICP/MS”. This document is intended to provide guidance to

those who are already familiar with the analysis of field samples for VOCs, carbonyls and metals.

Although the details described below are not entirely consistent with the Compendium of

Methods, items called out in this document are specific procedures needed to meet the data quality

goals of the Pilot monitoring program. This guideline is provided to assist states in implementation of the

Pilot monitoring network. This document is not policy and does not contain legally binding

requirements, nor is it regulation. While it presents recommendations and suggestions regarding

techniques for the measurement of toxic air pollutants for the Pilot Air Toxics Monitoring network, it

may not be appropriate for other situations. 

2.0 Method Detection Limit (MDL)

It is recognized that laboratories may obtain varying detection limits based on the procedure

used and level of the standard chosen for the method detection limit (MDL) study. It is also recognized

that data measured below the detection limit has a high level of uncertainty and in theory cannot be

reliably measured or quantitatively distinguished from zero or instrument noise. One of the key goals of

this pilot program is to gather measurement data for use in evaluating the issue of calculating annual

averages with data sets containing several observations less than the MDL. Annual-average

concentrations and comparisons to modeled estimates can be highly uncertain when a large percentage

of the measurements are below the MDL. To estimate annual average concentrations from monitoring

data, the data user generally substitutes 1⁄2 MDL for those observations reported as less than MDL. In
Pilot City Air Toxics Monitoring Study

February 2001 4

order to gather additional data to help improve the annual average determinations and shed light on the

quality of data at and below the MDL, “uncensored” data will be reported by the Pilot City

laboratories. An important facet of this “uncensored” data set will be the determination and reporting of

the uncertainty associated with data. The uncertainty estimates will be determined from data generated

by collocated monitors for precision.

A quote from the recent Science Advisory Board (SAB) review: “Just because an analytical

result is below the MDL does not mean that the laboratory has not been able to measure a value,

but rather that the measurement has less reliability than others that are above the MDL.

Subcommittee members stated that it is more useful to have laboratories report all data with

associated uncertainties than to have laboratories censor the data.” Although the values less than

the MDL cannot be reliably measured or quantitatively distinguished from zero, they have potential

value in computation of certain summary statistics (e.g. annual average concentration). The SAB review

can be obtained from the SAB web site under FY2000 full reports at

http://www.epa.gov/sab/fiscal00.htm 

The guidance given in 40 CFR Appendix B to Part 136, "Definition and procedure for

determination of the method detection limit"(See Appendix H of this document), will be used. Method

detection limit is defined as the minimum concentration of a substance that can be measured and

reported with 99% confidence that the analyte concentration is greater than zero and is determined

from analysis of a sample in a given matrix containing the analyte. 

2.1 Volatile Organic Compound (VOC) HAPs

Estimates of the method detection limits for the volatile organic compound (VOC) HAPs will be

determined in the following manner:

• A minimum of seven aliquots of the sample (individual canister samples) will be prepared and

each processed through the entire analytical method.

• The MDL should be determined on an annual basis, as a minimum, and when significant

instrument changes or maintenance occurs.

• Canisters should be humidified prior to MDL determination; refer to section on humidification

contained in this document.

• Individual canisters will be analyzed over a minimum period of 2 days (no maximum period is

specified). 
Pilot City Air Toxics Monitoring Study

February 2001 5

• All computations are made according to the defined method with the final results in the method

reporting units (ppbv for VOC).

• The guidance in 40CFR will be used to determine the suggested concentration ranges for the

individual canister (1 to 5 times the estimated detection limit), which should correspond to

approximately 0.1 to 0.5 ppbv. 

• Reasonableness of the calculated MDL will be determined using the iterative procedure as

described in 40 CFR Appendix B, section 7, which involves preparing additional standards at

the calculated MDL and analyzing. This may be difficult to implement with calculated MDLs as

low as 0.02 ppbv. Laboratory managers will be using the iterative procedure along with their

technical expertise and judgement to determine whether the calculated MDL is adequately

representative of the instrument capabilities.

2.2 Carbonyl Compounds

Estimates of the method detection limits for the carbonyl HAPs (formaldehyde and

acetaldehyde) will be determined in the following manner:

• A minimum of seven cartridges are spiked with derivatized compounds. Underivatized

compounds may be used at the discretion of the laboratory. 

• The MDL should be determined on an annual basis, as a minimum, and when significant

instrument changes or maintenance occurs.

• Individual spiked cartridges are extracted and analyzed no sooner than 24 hours after spiking. 

• Each cartridge is processed through the entire analytical method. All computations are made

according to the defined method with the final results in the method reporting units (total ug

converted to ppbv based on typical sample volume in L for a 24-hr sample).

• The guidance in 40CFR will be used to determine the suggested concentration ranges for the

individual cartridges (1 to 5 times the estimated detection limit), which should correspond to

about 0.03 to 0.15 μg per cartridge for formaldehyde and 0.05 to 0.25 :g per cartridge for

acetaldehyde (based on 500-L sample volume).

• Reasonableness of the calculated MDL will be determined using the iterative procedure as

described in 40 CFR Appendix B, section 7, which involves preparing additional standards at

the calculated MDL and analyzing. Laboratory managers will be using the iterative procedure

along with their technical expertise and judgement to determine whether the calculated MDL is
Pilot City Air Toxics Monitoring Study

February 2001 6

adequately representative of instrument capabilities.

2.3 Metals and Compounds

The detection limits stated in Table 1 of IO-3 for ICP/MS are sufficient to meet the needs of

the Toxics Pilot Monitoring program. Estimates of the method detection limits for the HAP metals will

be determined using 40 CFR Part 136, Appendix B and in a similar manner as described for the VOCs

and carbonyls. A minimum of seven strips from seven individual filters will be spiked with solutions

containing the core metal compounds at a level of 3 to 5 times the expected detection limit. Using the

detection limits given in IO-3, this corresponds to about 0.03 to 0.05 ng/L.

3.0 Uncertainty (Precision)

The SAB recommends that uncensored data be reported with an associated level of

uncertainty. For the Pilot monitoring program, this uncertainty will be determined from data collected

for precision estimates; however, a measure of uncertainty will not be established or reported with each

individual measurement. Procedures available to provide data for uncertainty and estimates of precision

include the use of collocated samples and replicate analyses. Precision is a measurement of mutual

agreement among individual measurements made under prescribed similar conditions. No special

adjustments, calibrations, or maintenance of the instruments should be made. Precision checks should

be made prior to any routine or special adjustments, calibrations or maintenance.

The types of precision determinations that will be made for the HAPs include:

• replicate analyses;

• collocated samples; and 

• inter- laboratory precision checks or “round-robin” analyses.

A minimum of 10% of the total number of samples will be collected in duplicate (collocated)

during the Pilot monitoring program for the urban area networks. For the small city/rural component,

collocated samples will be collected on a 1 in 12 day schedule for a minimum of 30 samples, as

resources allow. Replicate analyses will be performed on all collocated samples to provide “nested

duplicates” in order to provide an assessment of sampling and analytical precision for the study. 

Measures of precision will also be fulfilled using collocated samples that are processed and

analyzed by different organizations to provide inter-laboratory precision information for the
Pilot City Air Toxics Monitoring Study

February 2001 7

measurement process. A sample exchange program that involves inter-laboratory precision gives

important information concerning inconsistencies that may exist. Interpretation of these data must be

based on clear understanding and knowledge of how the data were obtained. Any differences in the

methodologies (i.e., detection limits, analytical column, calibration procedures, etc.) used to analyze the

exchange sample must be clarified in order to interpret and resolve any inconsistencies in the results.

Precision for inter-laboratory exchange samples is calculated in the same manner as precision for

replicate analyses or collocated samples. Round-robin sample analysis will occur twice over the course

of the Pilot program around the March and November time frame for VOCs and metals. Region 2,

Wisconsin, Michigan and South Coast Air Quality Management District (AQMD) have volunteered

and agreed to provide round-robin samples at this time.

A mechanism for providing round-robin samples for carbonyls has not been identified.

Technical limitations of sampling exist in relationship to collecting multiple, simultaneous ambient air

DNPH cartridges for this purpose. During the Pilot monitoring program, a round-robin comparison for

carbonyls will not be performed.

When evaluating the precision measurements, laboratories must consider each individual target

compound because precision will be compound-dependent with an influence of physical and chemical

properties (such as vapor pressure and reactivity). At very low concentrations, those at or below the

detection limit, agreement between measurements are expected to be poor. 

Data pairs where the compound is detected in both samples can be evaluated for percent

difference. To make a comparison of two values (i.e., duplicates or replicates) for precision, the

Relative Percent Difference (RPD) is a more meaningful statistic than relative standard deviation (RSD),

since the number of available measurements is only two.

Where:

Yi = larger of the two observed values

Xi = smaller of the two observed values
Pilot City Air Toxics Monitoring Study

February 2001 8

Measures of precision are to be reported with the measurement data, in order to provide the data users

with information to evaluate the uncertainty. If precision is calculated from three or more values (e.g.,

annual precision), RSD should be used.

RSD = (s / x) x 100

Where:

S = standard deviation of replicate values

X = mean of replicate values

The results from the various components of the quality assurance program are a vital part of the

database generated by the pilot projects. Unfortunately, AIRS does not currently accept this type of

information. It is the recommendation of the laboratory measurements work group that another group

be created to address data management issues and determine the components of the data package that

will be submitted by the Pilot City laboratories to the data analysis contractor. 

4.0 National Performance Audit Program (NPAP) - Bias

The NPAP will be unable to provide any audit or “check” samples due to reduction in budget

for FY2001. The option does exist to allow agencies to “buy in” to the program. If an agency has

resources for audit samples for carbonyl and VOC audits, contact the NPAP coordinator Mark

Shanis, EPA, OAQPS at 919-541-1323

5.0 Stability and Hold Times

5.1 Volatile Organic Compound (VOC) HAPs

The guidance given in TO-15 and data from the Office of Research and Development (ORD)

obtained as part of another toxics subcommittee are used to support the hold time for the core and max

pollutants at 30 days. The ORD data below gives the percent change over a 30 day period for each

pollutant. The concentration tested is given in parentheses. Methylene chloride seemed to be the least

stable in this data set.
Pilot City Air Toxics Monitoring Study

February 2001 9

Core List % Change

(concentration)

Max. List % Change

(concentration)

benzene 5% (0.6 ppbv) 1,2-dibromoethane 8% (1.2 ppbv)

1,3-butadiene 17% (2.5 ppbv) 1,3-dichloropropene 8% (0.5 ppbv)

carbon tetrachloride 12% (0.9 ppbv) 1,2-dichloroethane 9% (0.9 ppbv)

chloroform 9% (1.2 ppbv) 1,1,2,2-tetrachloroethane 12% (2.1 ppbv)

1,2-dichloropropane 15% (2.4 ppbv)

methylene chloride 27% (3.6 ppbv)

tetrachloroethylene 12% (1 pbbv)

trichloroethylene 13% (1 ppbv)

vinyl chloride 18% (0.8 ppbv)

5.2 Carbonyl Compounds

The specified hold time in TO-11A will be used for the Pilot program. DNPH-coated

cartridges will be extracted within 2 weeks and the extracts should be analyzed within 30 days. 

5.3 Metal Compounds

The hold time of 180 days as specified in IO-3 for filters will be used. Metals should be very

stable as long as the filters are handled and stored properly.

6.0 Measurement Procedures

6.1 Volatile Organic Compounds (VOCs )

Table 1 provides an outline of the specific procedures to be followed for the analysis of VOCs

by Compendium Method TO-15, “Determination of Volatile Organic Compounds in Air Collected in

Specially Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry, GC/MS.” 

A copy of this document is given in Appendix A. The procedures outlined in Table 1 also apply to the

use of Compendium Method TO-14A, “Determination of VOCs in Ambient Air Using Specially

Prepared Canisters with Subsequent Analysis by Gas Chromatography.” 
Pilot City Air Toxics Monitoring Study

February 2001 10

Table 1. VOC Analysis via TO-15A GC/MS for Air Toxics Pilot Monitoring Program

Item Description

Canister Type SUMMA or equivalent

Canister Certification No target analyte > MDL; 1 canister selected per

batch (batch size determined by laboratory)

Canister Transport Ambient conditions

Canister Storage Ambient conditions

Canister Hold Time 30 days

Method Detection Limit 40 CFR Appendix B to Part 136

Minimum of 7 low level canister standards

analyzed over minimum of 2 day period; MDL to

be determined on annual basis at minimum

Field Duplicates or Collocated Samples 10% of total samples for urban network or 1/12

for small city; 30 minimum per network

Analytical Instrumentation GC/MS or GC

Blanks

• Instrument blank Performed after instrument calibration

Replicate Analyses Performed on collocated (duplicate) samples

6.1.1 Humidification of VOC Canister Calibration Standards

The guidance on humidification is given in the PAMS Technical Assistance Document (TAD),

EPA/600-R-98/161, Section 2.3.4.3.1. This guidance (Appendix B) will be adopted for the toxics

program. The TAD gives information on procedures for determining the appropriate amount of water to

attain an adequate level of humidity in the sample canister without condensation. As stated in the TAD,

low pressure (30 psig) calibration standards prepared in canisters ideally should have a minimum

amount of water vapor ($20% relative humidity) to ensure sample integrity, but not enough water to

cause condensation of water vapor in the canister ($33% relative humidity). To achieve these

conditions in a 6-liter canister at 70°F, between 66 and 110 μL should be added. Calculations are

included in the guidance in order to determine the amount of water needed at varying pressures and

temperatures.
Pilot City Air Toxics Monitoring Study

February 2001 11

6.1.2 Canister Certification

Canisters will be cleaned in accordance with the laboratory’s normal procedures and TO-15.

Canisters will be acceptable for use if no target analyte is present at a level greater than the specified

MDL as determined in accordance with 40 CFR Part 136, Appendix B. One canister will be randomly

selected, or the canister known to be the “dirtiest” will be selected from each batch of canisters

cleaned. If the canister meets the acceptance criteria, the entire batch is considered acceptable and

therefore, ready for use. No additional flags or blank subtraction will be applied to the reported data.

6.2 Carbonyl Analysis

Table 2 outlines the specific procedures to be followed for the analysis of VOCs by

Compendium Method TO-11A, “Determination of Formaldehyde in Ambient Air Using Adsorbent

Cartridge Followed by High Performance Liquid Chromatography, HPLC“ (Appendix C).

Considerations were given to procedures also outlined in the compendium method, as well as those

provided in the Section 5, “Methodology for Determining Carbonyl Compounds in Ambient

Air”(Appendix D), of the PAMS Technical Assistance Document for the Sampling and Analysis of

Ozone Precursors, EPA/600-R-98/161; and draft guidance given in the “Guidance for Carbonyl

Measurements at PAMS” (Appendix E). 

Table 2. Carbonyl Analysis via TO-11A HPLC for Air Toxics Pilot Monitoring Program

Item Description

Cartridge Type DNPH-coated silica gel with ozone scrubber

Cartridge Lot Certification Minimum of 3 selected per Lot. Formaldehyde not

> 0.15 μg per cartridge

Acetaldehyde not > 0.10 μg per cartridge

Cartridge Sample Transport Ambient conditions

Cartridge Storage Refrigerated conditions

Hold Time Cartridges extracted within 2 weeks; extracts

analyzed within 30 days
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Field Blanks Frequency = (N)1⁄2; where N is the number of

field samples. < 0.15 μg formaldehyde and < 0.10

μg acetaldehyde

Trip Blanks Optional - normally used to resolve issues

identified from field blanks. 

Method Detection Limit 40 CFR Appendix B to Part 136

Minimum of 7 derivatized spiked cartridges;

extracted no sooner than 24 hours after spiking;

MDL must be determined on annual basis at a

minimum. If labs successful spiking underivatized

components then - OK

Field Duplicates or Collocated Samples 10% of total samples for urban network or 1/12

for small city; 30 minimum per network
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February 2001 13

Analytical Instrumentation HPLC (High performance liquid

chromatography)

Blanks

• Instrument blank

• Reagent blank

Performed after instrument calibration

Performed for each new Lot of reagent

Replicate Analyses Performed on duplicate (collocated) samples 

6.3 Metals Analysis

Table 3 outlines the specific procedures to be followed for the analysis of TSP (total suspended

particulate) filters by Inorganic Compendium Method IO-3.5, “Determination of Metals in Ambient

Particulate Matter Using Inductively Coupled Plasma/Mass Spectrometry, ICP/MS” (Appendix F).

Considerations were also given to procedures outlined in 40 CFR, Part 50 Appendix G, “Reference

method for the determination of lead in suspended particulate matter collected from ambient air”.

Consistency between Part 50, Appendix G and IO-3.5 were maintained where appropriate for filter

handling and other sampling-related procedures. For guidance related to the preparation of filter

material, Inorganic Compendium Method IO-3.1, “Selection, Preparation and Extraction of Filter

Material” is included in Appendix G.

6.3.1 Extractable versus Total Metals

Total metals (dissolution) indicates that the particulate and its matrix, as well as the filter, are

completely dissolved and results in a clear solution. This usually results in a fairly high level of solids in

solution and is often more difficult to analyze. Glass and quartz fiber filters would required the use of

hydrofluoric acid (HF) which means a more difficult and dangerous extraction process. “Extractables”

are just the compounds of the metal that dissolve into the solution you use for extraction. Different metal

compounds are extracted with nitric acid than with hydrochloric acid, or combinations, and the amounts

will vary depending on whether a hot plate, microwave or ultrasonic bath is used. Using different

extraction methods can complicate the interpretation of the data. Total metals determination is

considered more costly, difficult to perform and subject to greater background interference. Hot acid

extraction with HNO3 / HCl to determine “extractable” metals will be the procedure used for the

Toxics Pilot Monitoring Program. 
Pilot City Air Toxics Monitoring Study

February 2001 14

Table 3. TSP Analysis via IO-3.5 ICP/MS for Air Toxics Pilot Monitoring Program

Item Description

Filter type Quartz Filters. Based on results from filter contamination study

- glass fiber are also acceptable for the “core” pollutant list of

metals only

Filter QC per Method IO-3.1, Table 7 and Part 50, Appendix G

• Method (reagent) Blank

• Filter Lot Blank

• Matrix Spike

• Lab control (LC) blank

• Lab control sample (LCS)

1 per 24 samples; reagents only

Lots >500 (20-30 selected at random); Lots <500 (lesser

number can be taken) Filters analyzed for target species

1 per 20 samples; spiked filter

1 per extraction day; manufactured filter blank certified below

NIST traceable detection limits

1 per extraction day

Filter cutting procedure Pizza cutter preferred (as represented in IO-3.1, Figures 1 and

2). Strip width of 1 inch. Do not unfold filter as specified in

IO-3.

Filter Transport Ship under ambient conditions in protective envelope

Filter Storage 15-30°C

Filter Hold Time 180 days

Field Blanks 1/10 filters or 10%

Extraction procedure Hot acid extraction with HNO3 / HCl - extractable metals 

Extraction Efficiency Target 75-125% using NIST SRM 3087a, 2677a, or 1648 as

appropriate

Method Detection Limit 40 CFR Appendix B to Part 136 

Minimum of 7 filters; MDL must be determined on annual basis

as a minimum

Duplicate Filter Strips (Precision) 10 % of total samples for urban network or 1/12 for small city;

30 minimum per network
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Analytical Instrumentation ICP/MS

Blanks

• Instrument Blank

• Reagent Blank

• Rinse Blank 

As outlined in IO-3.5, page 3.5-11

Interferences - ICP/MS

• As interference by Argon on

ICP/MS

• Isobaric elemental

interference

• Abundance sensitivity

• Isobaric polyatomic Ion

interference

• Physical interferences

• Memory interferences

Several identified in IO-3.5, pages 3.5-4 for ICP/MS and

recommendations that labs should be aware of

7.0 Data Reporting

All data for the pilot study will be reported without "screening" or “censoring” the data below

detection or reporting limits. All measurements detected by the instrument will be reported with a

qualifying flag for those values below the lowest calibration level (LCL) - see below. The “7" data

qualifying flag has been established in the AIRS-AQS for this purpose. Only flag 7 will be used, which

also covers those values below the calculated MDL. Values analyzed for, but not detected, will be

reported as ND. Measures of precision as defined under the “Uncertainty” section of this document will

be reported along with the data set. Data reporting units to be defined by the Data Management work

group. A Data Management work group is being convened to discuss and clarify issues related to data

reporting. Please refer to the discussions and outcome of this work group for guidance on these issues.

7.1 Lowest Calibration Level (LCL)

Also often referred to as the minimum reporting level (MRL). Defined as the minimum

concentration that can be reported as a quantitated value for a target analyte in a sample following

analysis. For the purposes of the Pilot City study, data will be quantitated and reported below this level.

This will be the level at which the data below will be flagged indicating a level of uncertainty and still
Pilot City Air Toxics Monitoring Study

February 2001 16

useful for certain statistical purposes. This will be equivalent to the concentration of the lowest

calibration standard which can only be used if acceptable quality control criteria for this standard are

met. This is established at a level 3 times the MDL. Reference: Perchlorate in drinking water method

http://www.epa.gov/OGWDW/methods/met314.pdf.

8.0 Clarification of Terminology 

There appear to be many different acronyms in use for the quantitation of instrument sensitivity

and reporting of data. A sampling: PQL, MDL, LOD, LOQ, IDL, ... Many of the terms are used to

refer to the same thing and typically are used for water quality analyses; however, there are generally 2

distinct classes: detection limits and quantitation limits. For use in our discussions I decided to compile

some information from a variety of sources which describes some of the terminology (acronyms) used.

However, I do not try to address the issue of the variety of methods that can be used to determine

these detection or quantitation limits and how that impacts the values obtained by a specific laboratory.

Clarification: For the purposes of the Pilot Toxics monitoring network, we are using the

terms method detection limit (MDL) and lowest calibration level (LCL), which is very similar

to the MRL given below.

8.1 Detection Limits

8.1.1 Method Detection Limit (MDL)

EPA definition: the minimum concentration of a substance that can be measured and reported

with 99% confidence that the analyte concentration is greater than zero and is determined from analysis

of a sample in a given matrix containing the analyte. (Part 136, App. B) Determined by taking a

minimum of seven aliquots of the sample (in case of air sample analysis we are using individual canister

samples) to be used to calculate the method detection limit and process each through the entire

analytical method. Make all computations according to the defined method with the final results in the

method reporting units (ppbv).

Compendium Method TO-15 and TO-11A; Method 314.0 and 1631 (Bob Avery) also refer

to 40 CFR, Part 136, Appendix B

8.1.2 Limit of Detection (LOD)

Lowest concentration of an analyte that the analytical process can reliably detect. (Anal.

Chem., Vol. 52, No. 14, December 1980)
Pilot City Air Toxics Monitoring Study

February 2001 17

A number, expressed in units of concentration (or amount), that describes the lowest

concentration level (or amount) of the element that an analyst can determine to be statistically different

from the analytical blank. (Anal. Chem., Vol. 55, No. 7, June 1983 in reference to IUPAC definition in

Spectrochem. Acta B 1978, 33B, 242)

The lowest concentration of an analyte in a sample that can be detected but not necessarily

quantitated. Approximately 2 or 3 times the signal-to-noise (S/N) ratios. (LC/GC Vol. 16, No. 10,

October 1998 take from U.S. Pharmacopeia Conference, 1995)

The smallest observed signal (x) that with a reliability 1-" can be considered as being a signal

caused by the component to be measured. When the observed signal is smaller than x, however, it

cannot be stated that the component is absent. It can only be said with a reliability 1-$ that the

concentration of the component will be less than a certain value. (Quality Control in Analytical

Chemistry, Vol. 60, Kateman and Pijpers, John Wiley & Sons, 1981)

8.1.3 Detection Limit (DL) 

Minimum concentration of an analyte that can be measured above instrument background. 

Estimates of concentrations at which one can be fairly certain that the compound is present.

Concentrations below this limit may not be detected. Concentrations above this limit are almost

certainly detected. http://www.wcaslab.com/TECH/DETLIM.HTM

8.1.4 Instrument Detection Limit (IDL)

Lowest concentration that can be detected by an instrument without correction for the effects of

the sample matrix or method-specific parameters such as sample preparation. (Web reference dated

1/27/999 - www.pw1.netcom.com/~qaa/DETLIM.html- appears to be no longer available)

8.2 Quantitation Limits

8.2.1 Minimum Level (ML) 

The lowest level at which the entire analytical system must give a recognizable signal and

acceptable calibration point for the analyte. It is equivalent to the concentration of the lowest calibration

standard, assuming that all method-specific sample weights, volumes, and cleanup procedures have

been employed. Calculated by multiplying the MDL by 3.18 and rounding the result to the number

nearest to (1,2, or 5) x 10n, where n is an integer. Method 1631 (from Bob Avery at

http://www.epa.gov/ost/methods/1631final2.pdf)
Pilot City Air Toxics Monitoring Study

February 2001 18

8.2.2 Limit of Quantitation (LOQ) 

A minimum criterion or region for quantitation that should be clearly above the detection limit. 

The lowest concentration of an analyte in a sample that can be determined (quantitated) with acceptable

precision and accuracy under the stated operational conditions of the method. Approximately 10 times

the signal-to-noise (S/N) ratios. (LC/GC Vol. 16, No. 10, October 1998 take from U.S.

Pharmacopeia Conference, 1995)

8.2.3 Practical Quantitation Limit (PQL)

The lowest concentration of an analyte that can be reliably measured within specified limits of

precision and accuracy during routine laboratory operating conditions. The Agency has used the PQL

to estimate or evaluate the minimum concentration at which most laboratories can be expected to

reliably measure a specific chemical contaminant during day-to-day analyses of drinking water samples.

(EPA Office of Water web site www.epa.gov/ogwdw000/standard/review/methods.html)

Normally determined as 3 to 10 times the MDL and is considered the lowest concentration that

can be accurately measured , as opposed to just detected.

http://www.wcaslab.com/TECH/DETLIM.HTM

8.2.4 Minimum Reporting Level (MRL)

The minimum concentration that can be reported as a quantitated value for a target analyte in a

sample following analysis. This defined concentration can be no lower than the concentration of the

lowest calibration standard and can only be used if acceptable quality control criteria for this standard

are met. Established at a level either 3 times the MDL or at a concentration which would yield a

response greater than a signal-to-noise ratio of five. (Perchlorate in drinking water method 

http://www.epa.gov/OGWDW/methods/met314.pdf)
Pilot City Air Toxics Monitoring Study

February 2001

Appendix A

Compendium Method TO-15A, “Determination of Volatile Organic

Compounds in Air Collected in Specially-prepared Canisters and Analyzed

by Gas Chromatography/Mass Spectrometry, GC/MS

See: http://www.epa.gov/ttn/amtic/files/ambient/airtox/to-15r.pdf
Pilot City Air Toxics Monitoring Study

February 2001

Appendix B

Procedure for Humidification, Section 2.3.4.3.1 taken from the PAMS

Technical Assistance Document for the Sampling and Analysis of Ozone

Precursors, EPA/600-R-98/161

See: http://www.epa.gov/ttn/amtic/files/ambient/pams/newtad.pdf
Pilot City Air Toxics Monitoring Study

February 2001

Appendix C

Compendium Method TO-11A, “Determination of Formaldehyde in

Ambient Air Using Adsorbent Cartridge Followed by High Performance

Liquid Chromatography, HPLC“

See: http://www.epa.gov/ttn/amtic/files/ambient/airtox/to-11ar.pdf
Pilot City Air Toxics Monitoring Study

February 2001

Appendix D

DRAFT

Guidance for Carbonyl Measurements at PAMS 

prepared for EPA under contract 68-D-98-030 
DRAFT

Guidance for Carbonyl

Measurements at Photochemical

Assessment Monitoring

Stations (PAMS)

September 30, 1999

Prepared for EPA under

Contract 68-D-98-030

Work Assignment 2-02

Emissions, Monitoring, and Analysis Division

Office of Air Quality Planning and Standards

U.S. Environmental Protection Agency
ii

EPA Disclaimer

The information in this document has been funded wholly or in part by the United States Environmental

Protection Agency under Contract 68-D-98-030. It has not been subject to the Agency’s peer and

administrative review. Mention of trade names or commercial products does not constitute

endorsement or recommendation for use.
iii

Contents

Acknowledgment ........................................................... iv

Guidance for Carbonyl Measurements at Photochemical Assessment

Monitoring Stations (PAMS) ................................................... 1

I. Sampling System ................................................. 3

II. Cartridges ...................................................... 9

III. Analytical System ............................................... 12

IV. Blanks ....................................................... 17

V. Data Reporting .................................................. 19

VI. Concluding Remarks ............................................. 20

Figure

1. Control chart for plotting cartridge field blank values versus time ................... 22

Tables

1. Sampler quality control criteria checklist ..................................... 7

2. Analysis system quality control criteria checklist ............................... 14

3. Minimum number of blanks per field samples ................................. 19

4. Proposed checklist table for tracking cartridges ............................... 21
iv

Acknowledgment

We thank the many participants for their time in reviewing our outline and the draft document. 

The participants were staff involved in a previous work assignment involving a series of conference calls

to assess carbonyl measurements at PAMS. Their enthusiasm and willingness to share experiences and

knowledge were quite evident during the review process.
1

Guidance for Carbonyl Measurements

at Photochemical Assessment

Monitoring Stations (PAMS)

The determination of ambient concentrations of carbonyl compounds is a requirement of 40

CFR Part 58, Subpart E, enhanced ozone network monitoring programs.(1) The U.S. Environmental

Protection Agency (EPA) has established a Photochemical Assessment Monitoring Stations (PAMS)

program to provide routine measurements of selected volatile organic compounds (VOCs) and

carbonyl species. The PAMS program currently recommends the sampling and analysis of 55 VOCs

and three carbonyl compounds: formaldehyde, acetaldehyde, and acetone. The measurement of

acetone is now optional (see PAMSGRAM, Volume 16). For the measurement of carbonyl species,

States are required to obtain 3-hour and 24-hour integrated samples, at collection frequencies specified

for each type of enhanced ozone monitoring site. 

The measurement method for carbonyls in PAMS is based on U.S. EPA Compendium Method

TO-11A, which incorporates the use of sorbent cartridges coated with 2,4-dinitrophenylhydrazine

(DNPH) for sample collection.(2) The analyses are performed with high performance liquid

chromatography (HPLC). The two sorbents described in the compendium method are silica gel and

octadecylsilane bonded silica substrate (C18). For consistency, silica gel is recommended for use in

the PAMS program. For the PAMS program, 

carbonyl methodology is further explained in the Technical Assistance Document (TAD), which more

thoroughly discusses specific topics including monitoring instrumentation, ozone scrubbers, and

cartridge blanks.(3) The guidance provided here supercedes that given in the TAD where applicable.

Currently, numerous State, federal, and private laboratories are conducting carbonyl sampling

and analytical activities as part of the PAMS program. However, there are concerns about the existing

carbonyl database and data quality in general. As a result of these concerns, a series of conference

calls were conducted with several such groups, representing a wide range of procedures used during

the sampling and analysis efforts.(4) 

The mechanical integrity of field sampling devices and the lack of field audit and sampling

protocols are key issues for PAMS carbonyl measurements. One concern is the failure of aging
2

carbonyl sampling equipment as a result of leaks, which are often extremely difficult to detect and may

go unnoticed until data quality or other quality assurance/quality control (QA/QC) results indicate a

problem. Collocated sampling with duplicate equipment is one QA/QC approach to evaluate sampling

abnormalities, but State agencies often do not have the necessary extra equipment. Current

performance audits for the carbonyl sampling in the PAMS program employ a DNPH-silica gel

cartridge spiked with selected carbonyl derivatives. National Institute of Standards and Technology

(NIST) gas-phase carbonyl standards are not currently available for method calibration and bias

determinations. Consequently, until these standards are available, the integrity of carbonyl sampling

equipment cannot be completely tested.

Suitable QA/QC procedures are particularly important in light of discrepancies observed

among nominally identical carbonyl sampling and analytical systems operating at some of the PAMS

sites. The present PAMS carbonyl sampling methodology could benefit from the development of

procedures to enhance sampling precision and accuracy. Greater standardization of sampling and

analysis techniques should result in better data comparability from different sites, more consistent

assessment of data quality, and better estimation of seasonal and long-term trends in air quality. 

Detailed procedural guidance for existing PAMS equipment is critical to addressing the measurement

issues. 

The purpose of this document is to provide guidance for use by Agencies in order to obtain

more consistency in conducting carbonyl monitoring in the PAMS program. This document identifies

critical requirements for the collection and analysis of formaldehyde, acetaldehyde, and acetone, and

addresses the necessary QA/QC procedures to assure good quality data for the PAMS program. It

focuses on five subject areas: sampling system, sampling cartridges, analytical system, blanks and data

reporting. This document is not intended to replace TO-11A and the PAMS TAD, but is intended to

outline, clarify and emphasize important and critical aspects of the cartridge carbonyl methodology

essential in obtaining good quality data. The following specific guidance is given to help improve the

quality of the PAMS carbonyl data collected:
3

• Commercially available DNPH-cartridges and sampling equipment are to be used.

• Cartridge field blank subtractions are not be required.

• Flow rates for the 3-hr and 24-hr sampling are specified.

• Cartridge shipping procedures are clearly defined.

• Analytical information provided to EPA will be posted on the PAMS website (see

Section III.A.2).

• A routine ozone scrubber change-out schedule is specified.

The following sections provide the rationale and further details for implementation of these

PAMS carbonyl monitoring recommendations.

I. Sampling System

This section focuses on the physical requirements, the calibration, and the operation of the

carbonyl sampling system. At a minimum, the following components should be included in the PAMS

carbonyl sampler. These items are also described in Section 5.2 of the PAMS Technical Assistance

Document.(3)

A. Carbonyl Sampling System

• Carbonyl samplers should be constructed so that all material coming in contact with the

sampled air is glass, stainless steel, and/or TeflonTM.

• A heated inlet line to the sampler is strongly recommended to prevent condensation of

water and/or organic compounds. The material of construction for the inlet line should

be stainless steel, or TeflonTM. The elevated temperature of the inlet should be at -50

± 15EC.

• A denuder or cartridge type ozone scrubber is required to remove ambient ozone from

the sample stream. If a copper coil denuder is used, then it should be wrapped with a

cord heater and controlled to an elevated temperature (-50 ± 15EC) to prevent

condensation of water and/or organic compounds in the sampling line. 
4

• Inlet check valves, solenoid valves, or a multi-port rotary valve are recommended to

direct sample to, and to isolate, the individual sampling cartridges. Diffusive sampling

may occur if such valves are not present and operational. 

• A multiport cartridge assembly is recommended to support multi-event sampling and

allow for easy insertion and removal of DNPH sampling cartridges.

• The outlet side of the sample cartridge assemblies also must be equipped with check

valves (or equivalent) to isolate individual sampling cartridges.

• A mass flow controller or mass flow meter/control valve must be used to maintain

constant flow rate over the specified sampling period.

• An oil-less vacuum pump, capable of achieving a pressure drop of -25 inches Hg, is

necessary to draw sample through the sampling cartridge during collection.

• An event control and data acquisition device is required to allow unattended operation

of the collection system and to record sampling event information such as start and stop

times, collection flow rates, etc.

Although the above list consists of generally available standard components of air sampling equipment,

proper assembly requires tedious and time-consuming testing and evaluation. It is strongly

recommended that future users consider commercially available instruments that have been tested and

evaluated to meet carbonyl sampling requirements.

A separate commercial sampler also should be used for the 24-hour time integrated samples,

unless a single commercial unit is equipped to perform both types of sampling. At a minimum, the 24-hr

sampler should contain the same components as the 3-hr sampler except that the multi-port cartridge

assembly is not needed. Commercial samplers that can be automatically leak checked are highly

preferred.

Current commercial vendors of carbonyl sampling systems include:

• ATEC Atmospheric Technology, P.O. Box 8062, Calabasas, CA 91372-8062, (310)

457-2671

• Atmospheric Analysis and Consulting (AAC) Inc., 4572 Telephone Road, Suite 920,

Ventura, CA 93003, (805) 650-1642
5

• Millipore/Waters Chromatography, P.O. Box 9162, Marlborough, MA 01752-9748,

(800) 252-4752

• Scientific Instrumentation Specialists, P.O. Box 8941, Moscow, ID, (209) 882-3860

• SKC Inc., 334 Valley View Road, Eighty Four, PA 15330-9614, (800) 752-8472

• Supelco, Supelco Park, Bellefonte, PA 16823-0048, (800) 247-6628

• XonTech, Inc., 6862 Hayvenhurst Avenue, Van Nuys, CA 91406, (818) 787-7380

The mention of vendor names does not constitute endorsement or recommendation by the U.S. EPA. 

Each user should evaluate the system to make educated purchases and determine if it meets the

individual’s needs.

B. Requirements for an Ozone Scrubber

The EPA has previously determined through laboratory tests that ozone present in ambient air

interferes with the measurement of carbonyl compounds when using Method TO-11A. As stated in the

Technical Assistance Document,(3) ozone can interfere with carbonyl analyses in three ways:

• The ozone reacts with the DNPH on the cartridge, making the DNPH unavailable for

derivatizing carbonyl compounds

• The ozone degrades the carbonyl derivatives formed on the cartridge during sampling

• If the analytical separation is insufficient, the DNPH degradation products can coelute

with the target carbonyl derivatives.

The extent of interference depends upon the ambient concentration of both ozone and the carbonyl

compounds, and on the duration of sampling. Carbonyl compound losses can be as high as 50 percent

on days when the ambient ozone concentration reaches 120 ppbv.(3) As a result it is mandatory that an

ozone scrubber be used for carbonyl sampling in the PAMS program and that it be properly

maintained.

Two types of scrubbers have been developed ! the ozone denuder and the ozone cartridge

scrubber. Both scrubbers use potassium iodide (KI) as the scrubbing agent, and their designs
6

effectively allow for the removal of ozone at sampling flow rates up to 1 liter/minute. Details on the

equipment and preparation of these scrubbers are provided in the TAD, TO-11A, and PAMSGRam,

Volume 12 (5) documentation. Below is a brief description and recommended change-out time of each

device. 

The ozone denuder is a copper tube coated internally with a saturated solution of KI. The tube

is coiled and housed in a temperature-controlled chamber that is maintained at elevated temperature

(-50 ± 15EC). The elevated temperature prevents condensation of water vapor and organic

compounds in the coil during sampling. The ozone denuder as described in the TAD has a usable

lifetime of up to 100,000 ppb-hours. This lifetime period was determined during laboratory tests using

controlled relative humidity (RH) conditions. Denuder performance may be affected by the variable

pollutant and RH conditions in the ambient atmosphere. On a conservative basis, however, the

scrubber should be effective for up to 30 days of continuous ambient air sampling. To assure consistent

performance, replacement of the ozone denuder is recommended after the equivalent of 30 days of use,

e.g., six months of sampling on every sixth day. The scrubber is reusable, and the re-coating procedure

is described in the TAD.

The second type of ozone removal device described in the TAD is the cartridge scrubber. This

device is commercially available (e.g., Supelco, Waters) and is filled with approximately 1 gram of

ACS reagent grade KI (the cartridge is identical in size and shape to the precoated DNPH silica

cartridges). The scrubber cartridge is positioned at the sample inlet, just ahead of the DNPH-coated

cartridge. During high humidity/temperature conditions, it is recommended that the cartridge scrubber

be maintained at elevated temperature (~50 ± 15EC) to prevent condensation of water vapor and

organic compounds. According to the TAD, the theoretical removal capacity for ozone is 200 mg,

based upon the assumption of 100 percent consumption of KI. As a result, change-out of the cartridge

scrubber every three weeks is recommended.

C. Sample Probe Line and Connection to Primary Manifold

The primary sampling manifold must meet the criteria for the PAMS network. These criteria

can be found in Section 5.2.3 of the Technical Assistance Document.(3) The carbonyl sampler should

be connected to the primary manifold using a 1/4 inch O.D. heated line that is made of stainless steel or
7

TeflonTM. The ozone scrubber and carbonyl sample cartridge should be placed as close as possible to

the primary manifold. The carbonyl sampling line should be connected to the primary manifold at a

location that is downstream of the connection line used for VOC sampling (in order to minimize the

possibility of acetonitrile solvent back-diffusing into the VOC sampling line).

D. Calibration and Operation of Carbonyl Sampling System

Procedures for the calibration and operation of the carbonyl sampling system include

implementation of field check procedures, operation at specified flow rates, flow checks, and

employment of calibration gases to challenge the sampler. Table 1 provides a checklist to assess the

performance of the sampling system.

Table 1. Sampler Quality Control Criteria Checklist

Parameter Frequency Limits Corrective Action

Flow Check Each Sampling Event,

Pre- and Post-Checks

3 hr, 1.0 liter/minute

 (± 20%)

24 hr, 0.13 liter/minute

 (± 20%)

Repair/Exchange Unit 

Mass Flow Controller

(or mass flow meter)

Start, Midpoint, End of

Season

100 ± 10% (Reference

Meter)

Repair/Recalibrate Unit

Leak Check Before Each Sampling

Event

No Air Flow Recheck for Leaks,

Modify as Necessary

Sampler Blank Pre- and Post-Seasons <0.15 μg Formaldehyde/

Cartridge

Clean or Replace Sampler

Collocated Samples 10% of Field Samples ± 20 % Mark Samples as Suspect

Backup Cartridges(a) 10% of Field Samples # 10% of Total on Backup

Cartridge

Use Backup Cartridges

for All Samples

Trip Blanks Square Root of the

Number of Field Samples

<0.15 μg Formaldehyde/

Cartridge

Evaluate Sampling and

Analysis Procedures,

Purchase New Batch

Field Blanks Square Root of the

Number of Field Samples

<0.15 μg Formaldehyde/

Cartridge

Evaluate Sampling and

Analysis Procedures,

Purchase New Batch

Sampler Challenge 

(With Gas Mixtures)

Pre- and Post-Seasons 70 to 130% Recovery Clean or Replace Sampler
8

(a) Not needed if recommended flow rates are used; see Section I.D.2. 
9

1. Implementation of field check procedures

The TAD mentions several key activities that should be performed to assure proper

operation of the carbonyl sampler; however, re-emphasis and further details are

provided here. First, a leak check should be performed before each sampling event. 

The sampler should be on for at least 10 minutes prior to the leak test. The inlet line

should then be sealed and the mass flow controller (or mass flow meter) readout from

the sampler should drop to zero (within a few minutes). If leaks are detected, recheck,

tighten, and/or modify the system. Once the absence of leaks has been confirmed, the

inlet line is opened, and sampler flow should be checked with a NIST-traceable flow

meter to assure that the target flow rate is achieved (1.0 liter/minute for 3-hr sample,

0.13 liter/minute for 24-hr sample). 

Second, the mass flow controller for each sampler should be checked at the

start, at the midpoint, and at the end of each ozone season. For acceptability, the

calibration reading should be within 100 ± 10 percent of the reading from a NISTcertified flow meter. Deviations from this range should be noted and the mass flow

controller should be recalibrated or exchanged. Third, a sampling system blank check

should be performed as a pre- and post-season validation of the performance of the

sampler. This check is performed by obtaining a 3-hr cartridge sample while supplying

aldehyde-free air to the sampler inlet. It is recommended that aldehyde-free air be

generated by placing a DNPH cartridge at the inlet to the sampler. The sampler itself is

then operated at 1.0 liter/minute flow rate over its normal 3-hr sampling period. The

amount of aldehydes found in the resulting sample must originate from within the

sampling system and can be compared to ambient levels. The current requirement is

that the system blank check loading should be less than the Method TO-11A

acceptance criteria (<0.15 μg formaldehyde/cartridge). If not, the data need to be

qualified and the sampler should be cleaned/exchanged. The user should contact the

vendor for specific cleaning instructions.

As part of the normal QC activities for field sampling, it is recommended that

the following samples also be collected: collocated samples, backup cartridges, trip
10

blanks, and field blanks. However, if the flow rates of 1.0 liter/minute for the 3-hr

sampling and 0.13 liter/minute for the 24-hr sampling are used, then backup cartridges

are not necessary. Each of these blank types should be collected on a frequency as

shown in Table 1. Table 1 summarizes the critical QC activities and is intended to

replace Table 5-3 in the TAD for these nine parameters.

2. Operation at specified flow rates

For carbonyl measurements in the PAMs program, the target collection volume through

a DNPH cartridge is -180 liters of air. Thus, for the 3-hr sample, the required flow

rate is 1.0 liter/minute (± 20 percent). For the 24-hr sample, the required flow rate is

0.13 liter/minute (± 20 percent). As indicated in Table 1, if these flow rates are used,

then backup cartridges are not required.

3. Employment of calibration gases

Commercially available calibration cylinders have been prepared that contain stable

ppb levels of aldehydes. It is recommended that these calibration gas cylinders be

purchased from a specialty gas vendor and used to challenge the field sampling units. 

Percent recovered should be within 100 ± 30 percent of the delivered quantity of

carbonyl (based on the stated cylinder value). If the recovery values are outside this

range, appropriate troubleshooting procedures should be initiated. For additional

comparability, the cylinders should be exchanged across PAMS sites. 

II. Cartridges

This section is intended to re-emphasize important TAD and TO-11A information addressing

the acquisition, handling, shipping, and storage of DNPH-coated cartridges.

A. Preparation/Acquisition of Cartridges

Cartridges should be acquired in bulk quantities from commercial vendors. Preparation of

cartridges by individual laboratories is tedious, labor intensive, requiring clean room conditions, and is
11

not recommended. Noncommercial preparation is likely to result in more lot- to-lot variability than is

found in commercially prepared cartridges. This approach is counter-productive to improving

consistency in the PAMS program. Information on the cartridges such as vendor, quantity received,

date of receipt, lot number, and expiration date should be recorded in a laboratory note book.

Major commercial suppliers of DNPH-coated cartridges include:

• Supelco, Supelco Park, Bennefonte, PA 16823-0048, (800) 247-6628

• Millipore/Waters Chromatography, P.O. Box 9162, Marlborough, MA 01752-9748,

(800) 252-4752

• Atmospheric Analysis and Consulting (AAC) Inc., 4572 Telephone Road, Suite 920,

Ventura, CA 93003, (805) 650-1642

• SKC Inc., 334 Valley View Road, Eighty Four, PA 15330-9614, (800) 752-8472.

The mention of vendor names does not constitute endorsement or recommendation by the U.S. EPA. 

Each user should evaluate the cartridges to determine if they meet the program’s needs. 

The receiving laboratory should certify acceptability of the cartridge lot by following the blank

analysis procedure specified in the Technical Assistance Document.(3) For a minimum of three cartridge

lot blanks analyzed, the average blank value plus three times the standard deviation of the blank values

(i.e., 0 + 3s) must meet the criteria for acceptance set out in Method TO-11A, which are 

formaldehyde <0.15 μg/cartridge

acetaldehyde <0.10 μg/cartridge

acetone * <0.10 μg/cartridge

* Note: analysis for acetone is now optional for PAMS.

The certification blank value and lot number must be recorded in the laboratory record book and the

cartridge lot rejected and returned to the vendor if any acceptance value is not met.

B. Handling Cartridges

Biological processes produce carbonyl species from the skin and breath. Therefore, gloves

should be worn when handling cartridges. Polyethylene gloves (or equivalent) are recommended during
12

field usage of the cartridges. Nitrile gloves are recommended to protect the hands of the laboratory

chemist during the extraction of the cartridge with acetonitrile.

The field operator and laboratory chemist should minimize the time that unsealed cartridges are

exposed to the environment. Diffusive sampling does occur when the cartridge caps are removed and

can be significant depending upon background concentrations of the carbonyl species. DNPH is also

light sensitive, and the cartridges should be protected from direct light by retaining them in the sealed foil

pouch provided by the manufacturer or by covering with aluminum foil or similar material. Finally, to

further reduce the possibility of contamination, avoid writing directly on the cartridges or placing

adhesives onto the cartridges. 

C. Shipping and Storing Cartridges

At a minimum, the shipment and storage of cartridges for the PAMS program should follow the

guidelines indicated below:

• All cartridges should be stored in a dedicated refrigerator (4EC) until use ! adhere to

vendor’s expiration dates for use of cartridges.

• All cartridges should contain sealing caps (or plugs). Make sure caps are in place !

discard any cartridge found with a missing cap.

• All commercial cartridges should be transported inside their original shipping containers

(as shown in Figure 5 of the TO-11A document). Some commercial containers include

sealed foil pouches and glass culture tubes for individual cartridges; others include

polypropylene holders equipped with foam inserts for holding multiple tubes. 

• If the original shipping container is unavailable, friction-top metal cans should be used. 

The cans should be partially filled with a layer of activated charcoal.

• The shipping container should be padded with either polyethylene-air bubble padding

or clean laboratory tissue paper. Polyurethane foam or inked paper should never be

used as padding material.

• Cold packs are not required for cartridge shipment. Bulk shipment at room

temperature with second-day delivery is acceptable.

• Cartridges should be stored in a dedicated refrigerator (4EC) upon arrival at the

laboratory or field site.
13

III. Analytical System

This section focuses on the equipment requirements and the calibration and operation of the

DNPH-cartridge extraction and HPLC analysis systems.
14

The analytical system should include an adequate cartridge extraction apparatus as well as a

high performance liquid chromatographic system.

1. Cartridge extraction

The highest purity acetonitrile should be used to extract the sampled cartridges. Some

commercial manufacturers sell a carbonyl-free acetonitrile which is preferred. The

solvent lot should be analyzed upon receipt to determine the initial purity level, and then

periodically re-analyzed over the life of the bottle to track the aldehyde buildup over

time.

All glassware should be cleaned by rinsing with acetonitrile, then dried by heating to

60EC in a vacuum oven. The use of a nitrogen-purged glove box (bag) further reduces

the risk of contamination.

 

The sampled cartridge should be fore-flushed with acetonitrile to extract the derivatized

carbonyls. The alternative back-flush elution approach is not recommended because it

sometimes adds particulate materials also collected on the cartridge to the acetonitrile

extract solution. During analysis, the particles can cause premature sample valve failure

and can increase the column back pressure. Because the acetonitrile holdup volume is

~ 0.3 ml, an extraction volume of 5 ml is recommended.

 

2. HPLC analysis system

Section 11.3.1 of the TO-11A document specifies the HPLC operating parameters and

an isocratic elution program is adequate for sample analysis when formaldehyde is the

only carbonyl of interest. For more complex carbonyl samples, Section 14.3.1 of the

TO-11A document describes an HPLC gradient elution program that will resolve

acetaldehyde, acetone, propionaldehyde, and the higher molecular weight carbonyls. 

More recently, several commercial vendors have demonstrated similar separation
15

capabilities using their own specific brand of column and operating conditions. For

documentation and PAMS network consistency purposes, all PAMS measurement

groups are encouraged to provide the following information to Nash Gerald at

rice.joann@epa.gov:

 

• Name of Organization

• HPLC (type/manufacturer)

• Detector (type/manufacturer and wavelength)

• Data Handling System (type/manufacturer)

• Analytical Column (type/manufacturer)

• Guard Column (type/manufacturer)

• Column Operating Temperature

• Mobile Phase - Gradient Conditions (isocratic conditions)

• Solvents (manufacturer and lot number)

• Column Flow Rate/Column Head Pressure

• HPLC Run Time/Representative Calibration Run

• Sample Injection Volume

• Calibration Results ! MDL, Range, R2, etc.

This information will be tabulated and posted on the PAMS homepage at

www.epa.gov/oar/oaqps/pams. 

Although acetone is no longer a required target compound, it is recommended that

calibration data continue to be examined for the separation of the three C-3 carbonyl

species that may be present in the chromatogram (acrolein*, acetone, and

propionaldehyde). The resolution of these three peaks should be tracked over time to

evaluate column performance (for the lowest calibration mixture, each valley between

the three successive peaks should be less than 50 percent of the highest peak). Further

decreases in resolution and/or excessive column pressure buildup indicate the need for

column replacement or refurbishing.

* Note: Method TO-11A no longer considered applicable to acrolein.(6)

A. Calibration of Analytical System and Implementation of QA/QC Procedures 
16

To ensure consistency across the PAMS network, the following calibration procedures are

recommended. The frequency, acceptance criteria, and corrective actions associated with these

procedures are shown in Table 2. Many of the table items are updated parameters from Table 5-3 of

the TAD.

Table 2. Analysis System Quality Control Criteria Checklist

Parameter Frequency Limits Corrective Action

Multipoint Calibration Every 6 Months R2 > 0.99 Recalibrate

Check Standard Daily ± 10% Recalibrate

Method Detection Limit Annually <0.1 ppb or 0.22

Fg for a 180-liter

Sample

Check/Service Instrument

Replicate Injections Daily ± 10% Check/Service Instrument

NPAP Audit Samples One to Three

Times Per Year

-23% to +22% Recalibrate

Resolution of C-3 Carbonyl

Species(a)

Daily Valley Between

Peaks #50% of

Highest Peak

Change Column Program/

Change Column

Matrix Spike Each Lot ± 30% Check Against New

Matrix Spike

Laboratory/Extraction Blank Each Extraction

Batch

#Lot Certification

Blank

Check Laboratory

Processes

(a) Recommended for labs that continue to monitor the C-3 carbonyl species.
17

1. Calibration standards

Calibration standards should be purchased from commercial vendors. Material can be

purchased as solid DNPH-carbonyl derivatives or as dilute liquid mixtures. The liquid

mixtures are generally supplied in a range from 1 to 50 μg/ml as the carbonyl

compound. Further dilutions should be made with volumetric glassware.

2. Multipoint calibration

A working standard range from 10 ng/ml up to 2000 ng/ml should be targeted. A

multipoint calibration is recommended every six months, and a minimum of five

calibration points (including zero) should be used. Analyses at each point should be in

triplicate. A linear least-squares fit of the data should be conducted and an R2 value of

0.99 or better should be attained. The slope of the calibration curve for each

component provides a response factor (RF).

3. Calibration check standard

A separate, independent calibration standard near the expected levels of the target

carbonyl concentrations should be used for daily calibration checks of the analytical

system. The day-to-day variation of the components should be within ±10 percent of

the initial calibration value. If greater variability is observed, a fresh check standard

should be prepared. If results with the fresh standard deviate from the original

calibration curve slope by more than 15 percent, then a new multipoint curve should be

constructed. A plot of daily values on a Quality Control Chart should be made and

used by the analyst to check on long-term performance of the analytical system.

4. Method Detection Limits (MDLs)

The MDL determination should be done on an annual basis using the procedures

specified in the Code of Federal Regulations (40 CFR Part 136B).(7) In brief, a low

level standard is prepared at a concentration that is approximately two to five times the

estimated MDL. The standard is injected seven times. The average concentration is
18

calculated from the original calibration curve. The standard deviation and the

appropriate student t-value are used to calculate the MDL as described in the CFR.

C. Operation/Performance of Analytical System and Implementation of QA/QC 

Procedures 

1. Daily precision checks

Precision checks should be done on a daily basis and should include analyses of both

standard and sample. The precision (as relative standard deviation) should be within 10

percent, based on three replicate injections.

2. Chromatogram checks

Daily inspections should be made to check if retention times are drifting. A control

chart should be used to determine if trends are occurring. 

3. NPAP - spiked cartridges/performance audit samples

The National Performance Assessment Program (NPAP) is an ongoing program to

check analytical accuracy of participating laboratories. Cartridges spiked with know

amounts of liquid carbonyls (underivatized) are prepared and distributed to analytical

laboratories. All PAMS participants should perform analyses on the NPAP audit

samples. It is recommended that laboratories participate at least once per year. 

2. Matrix spike

A matrix spike test is recommended per cartridge lot. This procedure involves spiking

cartridges (at least three) with non-derivatized carbonyls, and provides an evaluation of

both the derivatization and the extraction processes. The underivatized carbonyls

should be obtained from commercial vendors. A target acceptance criterion is 70 to

130 percent recovery. If this criterion is not met, then the analyst should recheck the

matrix standard mixture against a new mixture.
19

5. Laboratory/extraction blank

Laboratory/extraction blanks should be analyzed for each batch of cartridges that are

extracted. The results from these analyzed samples will indicate the combined

cartridge, solvent, and glassware contamination level for each carbonyl compound. 

This QC activity will guide the analyst in verifying that laboratory operations are being

conducted appropriately.

6. Internal Standard (IS)

An internal standard, such as the cyclohexanone-DNPH derivative, is recommended as

another means of tracking instrument performance. The IS is not used for calibration

purposes but rather to track detector response and certify the injection of each sample

vial. The cyclohexanone derivative can be added to the acetonitrile prior to cartridge

extraction.

7. Acetonitrile purity

Acetonitrile used for extractions should be evaluated upon receipt and periodically

during use as described in Section III.A.1 of this document. A carbonyl free grade of

acetonitrile should be used.

IV. Blanks 

To ensure the quality of the data and to obtain more consistent results, the collection of sample

blanks is necessary. As indicated in the TAD, there are four types of blanks: lot certification blanks,

field blanks, trip blanks, and sampling system blanks. In this section, the purpose of each type of blank

is described, the number of blanks necessary is discussed, and finally, procedures to be used in

reporting the blank data are provided.

C. Types of Blanks
20

• Lot Certification Blanks ! Certification blanks consist of a minimum of three

laboratory blank cartridges that are eluted with acetonitrile and analyzed to verify

acceptability of a specified cartridge lot number from a commercial vendor. 

Certification blank analysis is required for each cartridge lot number. 

• Field Blanks ! Field blanks are blank cartridges that are sent to the field, connected

to the sampling system, and treated identically to the samples except that no air is

drawn through the cartridge. Field blanks are used to assess the background carbonyl

level for cartridges used during the ambient sample collection process.

• Trip Blanks ! Trip blanks are cartridges of the same lot number that are sent to the

field, stored, and returned to the laboratory with the sampled cartridges. Trip blank

cartridges are not connected to the sampling system. Trip blanks are optional and are

intended to be used to resolve contamination problems determined from the field

blanks. Trip blanks can be used to determine whether the contamination occurred

during the sampling process or during the shipping and storage process.

• Sampling System Blanks ! Pre- and post-season validation of the performance of

the sampling system is necessary. These system blanks are used to assess the

contamination level of the sampler itself, as described in Section I.D.1 of this document. 

B. Certification Blank

The blank value associated with the cartridge acceptance criteria is discussed here. The criteria

for certification are taken from TO-11A and are very conservative; most results will be well within

these values. For the certification blanks to be acceptable, the following criteria must be met:

• Formaldehyde: <0.15 μg per cartridge*

• Acetaldehyde: <0.10 μg per cartridge

• Acetone: <0.30 μg per cartridge.

* The equivalent formaldehyde concentration for a 180-liter sample volume is 0.679 ppbv.

If the analysis of the three unsampled DNPH cartridges provide blank values with a mean plus three

standard deviations (0 + 3s) that is less than the above criteria, then the sample lot is acceptable. If the

value is above the criteria, then additional blanks must be processed. The sample lot cannot be used
21

unless the above criteria have been met. Field blank values should be consistently less than 2 times the

mean value of the certification blanks (i.e., < 20).

A sampling system blank also should be determined for each sampler prior to and after the

ozone season. To collect a sampling system blank, the system is challenged with carbonyl- free air. 

Carbonyl-free air can be generated by passing the incoming air through acidic DNPH solution in a

bubbling device, or through DNPH-coated cartridges. Alternatively, air containing a predetermined

level of carbonyls can be used. The same sampling procedure used for actual samples should be used

for the system blank (e.g., flow rate, time - see Section I.D.2). 

C. Frequency of Obtaining Blank Data

As discussed earlier, a minimum of three laboratory blanks from each lot of DNPH cartridges

are required for certification of that lot. Also, as stated in the TAD, it is recommended that a number of

cartridges equal to the square root of the total number of samples be analyzed as field blanks. Table 3

gives a few examples of the minimum number of blanks per field samples. Table 4 provides a guideline

for tracking the certified and field blanks over time. Critical information for the table includes the

vendor; date of receipt of cartridge; lot number; expiration, extraction, and analysis dates; and lot

certified and field blank values.

Table 3. Minimum Number of Blanks Per Field Samples

Number of 

Field Samples

Lab Blanks for 

Certification of Sample Lot 

Field Blanks Required

(square root of sample size)

50 3 7

100 3 10

200 3 14

V. Data Reporting 

The collection and analysis of field blanks should be distributed over the entire period that the

cartridge lot is used for ambient air sampling. The data from Table 4 should be used to evaluate
22

background carbonyl buildup over time. A trend plot also can be used to track background values

versus time. The trend plot should show the certified blank mean value and the ± 3s level for that

particular lot. Field blank values are then plotted in the trend plot as they become available (see Figure

1).

The PAMS Technical Assistance Document (Section 5.3.2) requires subtraction of the lot average field

blank value from all samples. However, this approach can sometimes obscure the relative magnitude of

the blanks and sample results. As a result, for data reduction and reporting purposes, field blank

subtraction for PAMS should not normally be done. The following approach is recommended:

1. If the field blank values are all within the 0 ± 3s range, then blank subtraction is not

necessary. Field blank results must be reported with the appropriate data set.

2. If the field blank mass loadings exceed the 0 ± 3s range but are still less than the 

certification criteria (e.g., formaldehyde <0.15 μg per cartridge), then blank subtraction

is again not necessary. However, it is recommended that a new sample lot of cartridges

be integrated into the program immediately. Field blank results must be reported with

the appropriate data set.

3. If the field blank mass loadings exceed the certification criteria (e.g. formaldehyde

>0.15 μg per cartridge), then blank subtraction should be done and the sample lot of

cartridges should be phased out as quickly as possible. Field blank data must be

reported with the appropriate data set.

VI. Concluding Remarks

The purpose of this document is to provide more consistency in conducting carbonyl monitoring

in the PAMS program. This document focuses on improving consistency in five subject areas: sampling

system, sampling cartridges, analytical system, blanks and data reporting. This is considered a working
23

document and PAMS participants are encouraged to provide comments and suggest improvements. 

Please send any comments to : rice.joann@epa.gov.

 
24

Table 4. Proposed Checklist Table for Tracking Cartridges

Vendor

Date of

Receipt

Lot

Number

Expiration

Date

Extraction

Date

Analysis

Date

Lot

Certified

Blank

Value

Field Blank

Value
25

Figure 1. Control Chart for Plotting Cartridge Field Blank Values Versus Time

 (Certified blank mean is shown as the solid line with dashed

 lines as the +/- 3 standard deviation values)

0

10

20

30

40

50

60

70

80

90

100

0 2 4 6 8 10

Day

nanogram loading, formaldehyde
26

References

1. Code of Federal Regulations. Title 40, Part 58. Ambient Air Quality Surveillance, Final Rule

Federal Register, Vol. 58, No. 28, February 12, 1993.

2. Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient

Air–TO-11A, U.S. Environmental Protection Agency, EPA/625R-96/010b, Research Triangle

Park, NC, January 1997.

3. Technical Assistance Document for Sampling and Analysis of Ozone Precursors, U.S.

Environmental Protection Agency, EPA/600-R-98/161, Research Triangle Park, NC,

September 1998.

4. Assessment of Carbonyl Measurements at Photochemical Assessment Monitoring Stations

(PAMS) – Conference Calls, Battelle Report to U.S. EPA, Contract 68-D-98-030, Work

Assignment 2-03, January, 1999.

5. The Use of KI-coated Copper Ozone Denuders for Carbonyl Measurements at PAMS. EPA

PAMSGRam, Volume #12, October 13, 1998.

6. Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air -

Second Edition, ADDENDUM, April 15, 1999.

7. U.S. Environmental Protection Agency. Code of Federal Regulations. Title 40, Chapter 1, Part

136, Appendix B. Office of the Federal Register, July 1, 1987.
Pilot City Air Toxics Monitoring Study Guidelines DRAFT

February 2001

Appendix E

“Methodology for Determining Carbonyl Compounds in Ambient Air”,

Section 5 from the PAMS Technical Assistance Document for the

Sampling and Analysis of Ozone Precursors,

 EPA/600-R-98/161

See: http://www.epa.gov/ttn/amtic/files/ambient/pams/newtad.pdf
Pilot City Air Toxics Monitoring Study Guidelines DRAFT

February 2001

Appendix F

Inorganic Compendium Method IO-3.5, “Determination of Metals in

Ambient Particulate Matter Using Inductively Coupled Plasma/Mass

Spectrometry, ICP/MS”

See: http://www.epa.gov/ttn/amtic/files/ambient/inorganic/mthd-3-5.pdf

 
Pilot City Air Toxics Monitoring Study Guidelines DRAFT

February 2001

Appendix G

Inorganic Compendium Method IO-3.1, “Selection, Preparation and

Extraction of Filter Material”

See: http://www.epa.gov/ttn/amtic/files/ambient/inorganic/mthd-3-1.pdf
Pilot City Air Toxics Monitoring Study Guidelines DRAFT

February 2001

Appendix H

40 CFR Appendix B to Part 136 - “Definition and Procedure for 

the Determination of the Method Detection Limit”, Revision 1.11




TECHNICAL REPORT DATA

(Please read Instructions on reverse before completing)

1. REPORT NO.

 EPA-454/R-01-003

2. 3. RECIPIENT'S ACCESSION NO.

4. TITLE AND SUBTITLE

 Pilot City Air Toxics Measurement Summary

5. REPORT DATE

 2/2001

6. PERFORMING ORGANIZATION CODE

USEPA/OAQPS/EMAD/MQAG

7. AUTHOR(S)

 

 Joann Rice

8. PERFORMING ORGANIZATION REPORT NO.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

 U.S. Environmental Protection Agency

 Office of Air Quality Planning and Standards

 Research Triangle Park, NC 27711

10. PROGRAM ELEMENT NO.

11. CONTRACT/GRANT NO.

 NONE

12. SPONSORING AGENCY NAME AND ADDRESS

 Director

 Office of Air Quality Planning and Standards

 Office of Air and Radiation

 U.S. Environmental Protection Agency

 Research Triangle Park, NC 27711

13. TYPE OF REPORT AND PERIOD COVERED

Measurement summary

14. SPONSORING AGENCY CODE

EPA/200/04

15. SUPPLEMENTARY NOTES

16. ABSTRACT

This summary of guidelines provides agreed-upon measurement procedures needed to provide consistent data for the FY2000

National Air Toxics Pilot Monitoring Program, initiated by EPA through the S103 Grant Process. Although the details of the

procedures herein are not entirely consistent with the Compendium of Methods, items called out are specific to the data quality

goals of the Pilot Monitoring Program.

This document is not policy and does not contain legally binding requirements, nor is it regulation. While it presents

recommendations and suggestions regarding techniques for the measurement of toxic air pollutants for the Program discussed

above, it may not be appropriate for other situations. This document is intended for use by those already familiar with the analysis

of field samples for volatile organic compounds (VOC’s), carbonyl compounds and metals.

 

17. KEY WORDS AND DOCUMENT ANALYSIS

a. DESCRIPTORS b. IDENTIFIERS/OPEN ENDED TERMS c. COSATI Field/Group

VOC Particulates

carbonyls toxic monitoring

metals Replicates, duplicates, field blanks

MDL filters

TSP

Air Pollution control

Air Pollution monitoring

18. DISTRIBUTION STATEMENT

 Release Unlimited

19. SECURITY CLASS (Report)

 Unclassified

21. NO. OF PAGES

65

20. SECURITY CLASS (Page)

 Unclassified

22. PRICE