### APPENDIX III

MATES III

FINAL REPORT

MATES III Monitoring and Laboratory Analysis Protoc ol

Authors Rudy Eden

Steve Barbosa

Solomon TefferaMATES III Final Report

Appendix III-1 

### MATES III

APPENDIX III

MONITORING AND LABORATORY ANALYSIS PROTOCOL

March 2004

Science and Technology Advancement South Coast Air Quality Management AQMD

Draft Approved for Review Date Approved

Rudy Eden
Senior Manager, Laboratory Services Applied Science & TechnologyMATES III Final Report

Appendix III-2 DISCLAIMER

Any or all reference made in this Protocol to a spe cific product or brand name does not constitute an endorsement of that product or brand by the Sout h Coast Air Quality Management District.MATES III Final Report

Appendix III-3 Table of Contents

List of Figures

List of Tables List of Appendices

Chapter 1.0 Introduction 1.1 Background

Chapter 2.0 Monitoring Equipment

2.1 Introduction 2.2 Equipment Characteristics 2.2.1 Siting 2.2.2 Acceptance Testing

2.2.3 Calibration 2.2.4 Sample Pickup 2.2.5 Trouble Shooting 2.2.6 Repair 2.3 Sampling Equipment

2.3.1 XonTech 910A and 912 2.3.1.1 XonTech 910A, Description 2.3.1.2 XonTech 912, Description 2.3.1.3 Pre-Testing

2.3.1.4 Cleanliness Check 2.3.1.5 Sample Pickup

2.3.2 XonTech 920 and XonTech 924 2.3.2.1 Description 2.3.2.2 Operation 2.3.3 ATEC 800 Sequential Sampler 2.3.3.1 Description 2.3.3.2 Operation

2.3.4 MET One SASS 2.3.4.1 Description 2.3.4.2 Module and Media Description

2.3.5 Gil Solent 2 Axis Ultrasonic Anemometer 2.3.5.1 Description 2.3.5.2 Siting

2.3.5.3 Installation 2.3.5.4 Telemetry Interfacing

2.3.5.5 Routine Service 2.3.5.6 Diagnostics

2.3.5.7 Calibration 2.3.5.8 Data Handling 2.3.6 Graseby-GMW 1200 PM 10 Sampler 2.3.6.1 DescriptionMATES III Final Report

Appendix III-4 Chapter 3.0 Laboratory Procedures

3.1 Introduction 3.2 Sample Handling 3.2.1 Canister Cleaning

3.2.2 Field Canister Use 3.2.3 Sample Distribution in the Laboratory 3.3 Analysis Methods 3.4 Sampling and Analysis - Table 1 Compounds 3.5 Sampling and Analysis - Table 2 Compounds 3.6 Sampling Schedule Chapter 4.0 Quality Assurance and Quality Control

4.1 Introduction 4.2 Objectives

4.3 Procedures 4.3.1 Quality Assurance Procedures 4.3.2 Quality Control Procedures

4.4 Documentation

4.5 Data Review

Chapter 5.0 Data Processing and Reporting

5.1 Introduction 5.2 Data Base Compilation 5.3 Periodic Reports 5.4 Final Report

Glossary Acronym ListMATES III Final Report

Appendix III-5 List of Tables

Table 2-1 Performance Specifications Gill Solent 2 Axis Ultrasonic Meteorological Anemometer Specifications Table 3-1 Mobile Platform Sampling Schedule Table 4-1 QA/QC Data Quality Objectives

List of Figures

Figure 2-1 Graseby-GMW PM 10 Sampler, Model 1200 with Two-Stage, SSI Head

List of Appendices

Appendix A Proposed Table 1 Air Contaminants for Inclusion in the Measurement Program Appendix B Proposed Table 2 Air Contaminants that P otentially May Be Monitored on a

Limited Basis Appendix C Size-Selective Inlet PM 10 Sampler Envelope Appendix D Monthly WSD Quality Control Maintenance Check Sheet Appendix E High Volume Monthly Control Maintenance Check Sheet Appendix F MATES III Sample Log Appendix F-1 Microscale Sample Log Appendix G VOC Canister Tag Appendix H Method Description for Sampling and Anal ysis of Carbonyls by HPLC at the

AQMD Laboratory Appendix I Method Description for Sampling and Anal ysis of Elements by Energy Dispersive

X-Ray Fluorescence Spectrometry at the AQMD Laborat ory Appendix J Method Description for Sampling and Anal ysis of Elements by Energy Dispersive

X-Ray Fluorescence Spectrometry at the AQMD Laborat ory Appendix K Method Description for Sampling and Anal ysis of Organic and Elemental Carbon

by Thermal/Optical Carbon Analyzer at the AQMD Labo ratory Appendix L QA/QC Matrix Summary Appendix M Method Description for Sampling and Anal ysis of VOCs by GC/MS at the AQMDMATES III Final Report

Appendix III-1 Chapter 1.0

Introduction

This protocol document provides detailed informatio n about the procedures and processes required to conduct the field measurement element o f the Multiple Air Toxics Exposure Study III (MATES III).

1.1 BACKGROUND In 1998, the South Coast Air Quality Management Dis trict (AQMD) conducted an intensive ambient air toxics monitoring program, th e Multiple Air Toxics Exposure Study (MATES II). The objective of MATES II was to estab lish a baseline of existing air toxics ambient emissions, exposure and risk level data and an assessment of model accuracy. The AQMD conducted MATES II over a one-year period at ten sampling sites in the South Coast Air Basin (Basin). The MATES II Final Report was approved by the AQMD

Board in March 2000 1

.

The microscale monitoring element of MATES II was c onducted to determine if communities were experiencing localized hot spots n ot otherwise identified through the regional modeling. Microscale sampling was conduct ed over six-week intervals at selected locations throughout the Basin using three mobile sampling platforms. During the year-long monitoring period, the platforms were deployed to collect ambient toxics

measurements.

For MATES III, specific compounds will be sampled a nd analyzed. These compounds are identified in Appendices A and B. Compounds li sted in Table 1 (Appendix A) will be measured on a routine basis, while compounds listed in Table 2 (Appendix B) will undergo more limited measurement and sampling due t o methodological limitations, high cost of analysis, or other limitations.

Field sampling will begin in April 2004 and continu e for a minimum of one year. This document describes the monitoring, laboratory analy sis, quality control (QC), and quality assurance (QA) activities necessary to support both the regional and microscale sampling

programs.

1 South Coast Air Quality Management District (2000)

. MATES II Final Report . Diamond Bar, CAMATES III Final Report

Appendix III-2 Chapter 2.0 Monitoring Equipment

2.1 INTRODUCTION

For the purposes of this protocol, the descriptions and operational and maintenance procedures of the following equipment used in MATES III sites will be delineated.

Sampler Type Vendor and Model Number

Volatile Organic Compounds (VOC) XonTech 910A/ 912

Metals; Carbonyls XonTech 920 and 924

Carbonyls ATEC 800 Sequential Sampler

PM 2.5 Speciation Air Sampling System Met One Instruments SASS

Wind, Speed, and Direction (WSD) Gill Solent 2 Axis Ultrasonic Anemometer (Met-One)

PM 10 Graseby-GMW 1200 PM 10 Sampler

The siting, acceptance testing, and calibration fun ctions for each type of equipment identified above are basically identical. Therefor e, these functions are defined below. Non-generic functions will be discussed under each equipment heading.

2.2 EQUIPMENT CHARACTERISTICS

2.2.1 Siting

A) Monitoring site selection criteria will be the s ame in most regards whether the site

will be used for a fixed or mobile site. Site unif ormity will be achieved to the greatest degree possible. Descriptions will be prepared for all sampling sites. The description should include, at a minimum, the type of ground su rface, the direction, distance, and approximate height to any airflow obstruction, and the direction and distance to any local pollutant sources.

B) The sampler platform will be located in an area with unobstructed airflow, especially in the direction of any recognized sources of the s ampled compounds. Turbulence and eddies from obstructions will cause non-represe ntative results. The distance between the obstruction and the sampler should not be closer than two times the height of the obstruction.MATES III Final Report

Appendix III-3 C) Locations unduly influenced by nearby sources or activities or where reactive surfaces may cause chemical changes in the air sampled will be avoided. Micrometeorological influences caused by nearby hills, b odies of water, valley drainage flow patterns, etc. will be taken into consideratio n.

D) The recommended intake probe height for criteria pollutants is 3 to 15 meters above ground level as near breathing height as possible, but not where a building is an obstruction or the equipment is easily vandalized.

E) The probe should extend at least two meters away from the supporting structure. If the probe is located on a building, it must be moun ted on the windward side.

2.2.2 Acceptance Testing

Acceptance testing will be performed on all instrum entation for approximately one month after receipt. After acceptance testing is conduct ed on the instruments, they will be deployed in the field and ambient sampling will com mence. Acceptance testing will be conducted through the following steps:

A) All instruments will be carefully unpacked from their shipping containers and checked for completeness, broken parts, and correct subunits.

B) The units will be assembled according to manufac turer guidelines and prepared for
start-up.

C) The flowrate/flow meter portion of the pneumatic system will be checked using the most appropriate calibration-transfer standard to v erify the operating flow/flowrate.

D) Timer accuracy will be evaluated by comparing it to an elapsed-timer standard. All timers must hold their accuracy to ± 5 minutes over a 24-hour period.

E) Any deficiency will be corrected following the m anufacturer’s procedures.

F) Each microscale site will be operated for an int ensive six to eight-week sampling period. Following sampling, each microscale monito ring mobile platform will be loaded on the transport vehicle and moved to the ne xt sampling site. The lease agreement for each monitoring site will be executed for a minimum eight-week period. Within this contractual time frame, the te mporary power can be hooked up, temporary fencing installed and all samplers at the new site can be calibrated prior to beginning the next intensive eight-week sampling pe riod. Sampling will be

conducted at each microscale site on the same one-d ay-in-three schedule as the

MATES III fixed sites.MATES III Final Report

Appendix III-4 2.2.3 Calibration

At each sampling site, final dynamic calibration wi ll be performed on each analyzer prior to the start of the intensive six-week sampling per iod. At the end of this sampling period, an “As Is” dynamic calibration will be performed on each analyzer to ascertain the amount of analyzer drift.

2.2.4 Sample Pickup

The AQMD Senior Chemist sample custodian will distr ibute the sampling media to the field technician. Filters and carbonyl cartridges will be transported in coolers with blue ice, and the canisters will be kept capped at all t imes during transportation. Once the filter and carbonyl cartridge has been used to coll ect a sample, they must be refrigerated until they are returned to the AQMD. The sampling media will be returned to the Senior Chemist sample custodian as soon as possible follow ing sampling.

2.2.5 Troubleshooting

A maintenance guide based on the equipment manufact urers’ suggested operating procedures will be available for each instrument. If an instrument falls out of the correct operating range, or if there is a component failure , the operator will immediately place a call to the AQMD STA/AM Support and Repair Section to schedule a repair.

2.2.6 Repair

Due to anticipated failure of standard components s uch as pumps and flow controllers, the AQMD will warehouse standard component spare pa rts. Since the sampling time at each location will be relatively brief, repair of m icroscale monitoring platform samplers will receive priority.

2.3 SAMPLING EQUIPMENT

2.3.1 XonTech 910A and 912

2.3.1.1 XonTech 910A - Description

The XonTech 910A air sampler is designed to take ai r samples at a constant flow rate for a known sampling period. It is durable, s erviceable and accurate making it useful for sampling a wide variety of gases. Its c ompact, constructed simply, and offers long term reliability.

Specifically, the 910A sampler takes air from the s ample inlet and injects it into a canister at a constant flow rate for the preset per iod of time. Excess air is exhausted through a bypass exhaust. The constant flow rate a nd elapsed time allow the operator to calculate the integrated air sample vol ume. The sample will be pumpedMATES III Final Report

Appendix III-5 through a metal bellows pump that develops sufficie nt pressure to control the flow with a mass flowmeter. The XonTech 910A is operate d according to the guidelines

set forth in XonTech’s Model 910 Toxic Air Sampler Operations Manual 2

.

2.3.1.2 XonTech 912 - Description

The XonTech 912 adapter may be added to the XonTech 910A to enhance sampling capability over a reduced period of time. It canno t operate independent of the 910A. It is designed to route gas samples to a maximum of 16 canisters. An internal time base can be used to step a rotary valve from canist er to canister at a user-selected rate. The 912 will also accept timing signals from the model 910A. The XonTech 912 adapter is operated according to the guidelines set forth in XonTech’s Model 910 Toxic Air Sampler Operations Manual 3

.

2.3.1.3 Pre-Testing

All canister samplers will be test run at the AQMD headquarters to assure proper operation. Most samplers are also field tested dur ing field sampling.

2.3.1.4 Cleanliness Check

To perform a system bias check, ultra-pure air or n itrogen will be injected into the sample manifold to fill one, 3-hour canister. Addi tionally, the 24-hour sampler can be tested by maximally increasing its sample flow t o fill a canister in approximately

6 hours. A field blank will be filled at the site by flowing pure air or nitrogen into an evacuated cylinder. A difference of less than 1 pa rt per billion (ppb) per compound between the field blank and the bias samples indica tes that the system is non-biasing (non-contaminated). A value greater than 1 ppb per compound requires corrective action. A system bias check will be repeated until all biases are demonstrated to be eliminated. The AQMD’s Ambient Monitoring Support Group will perform system repairs. This group will assemble, leak check, dis assemble, and clean the sample manifold, and the Auditing Group will calibrate the mass flow controller (MFC) for

flow.

2.3.1.5 Sample Pickup

An AQMD Instrument Specialist will pick up clean VO C canisters in the Laboratory.

Evacuated canisters will be transported by vehicle to the respective ai r monitoring stations. Each canister has a tag attached (Append ix G). This tag will be completed to contain the following information: sample site, operator initials, sample date, and canister number in sampling sequence. The air moni toring station operator should complete this tag once the canister is set up for s ampling. Once the canister is filled and disconnected from the 910A or 912 sampler, and prior to returning the sampled

2 XonTech, Inc. (1987). Model 910 Toxic Air Sampler Operations Manual . Van Nuys, CA: Author.

3 Ibid.MATES III Final Report

Appendix III-6 canister to the Laboratory, the canister number, st art vacuum, end pressure (psig), and elapsed time will be recorded on the canister s ample log (Appendix F and F-1). The time on the QC chart must also be checked and a djusted. This value must be

within ± 10 minutes of actual Local Standard Time. The canister will be delivered to the Senior Chemist sample custodian as soon as poss ible.

2.3.2 XonTech 920 and XonTech 924

2.3.2.1 Description

The Model 920 and equivalent Model 924 Toxic Air Sa mplers are designed to collect ambient air particulate samples on a variet y of filter materials and sorbent media in unattended field use. These samples will be brought to the AQMD headquarters for Laboratory analysis. The sampler precisely controls the sampling time and flowrate through each sampling head using a microprocessor and mass flow controller (MFC). Sampler design is modular to fac ilitate installation of individual sampling channels. Each sampler may accommodate ei ght sampling channels for two types of sample collection media: one that acce pts 37 or 47 millimeter filters and another that accepts sorbent tubes.

The sampler consists of three modules, each contain ed in a separate enclosure. The heart of the system is the control module. This mo dule contains the microprocessor, controller, mass-flow controllers, and front panel, displays, printer, and keypad. The

difference between the Model 920 and 924 is the ele ctronics have been upgraded to reflect the increase in microprocessor functionalit y presently available that was not available in the circa 1995 Model 920. The samplin g module is equipped with isolation valves that protect the sampling media fr om passive sampling before or after sampling or sample loss after sampling. The sampling module and the pump module have not changed between the Model 920 and 9 24. The sampling inlet height is 1.2 meters above ground level. The third element of the sampler is the pump module. It contains the vacuum pump that prov ides adequate capacity for simultaneous operation of three, 30 liters per minu te (lpm) and 200 cubic centimeters per minute (ccm) sampling channels.

2.3.2.2 Operation

To use the sampler, the operator will insert the sa mple filter cassette or sorbent tube into the sampling head and will key in the filter o r sorbent head number. Start and stop times, and flow rates are pre-programmed or ca n be manually input. Following the sampling period, a report is automatically prin ted which may be removed from the printer and submitted to the Laboratory with th e filter for analysis.

When the sampling period concludes, a report is aut omatically printed. This report is removed from the printer and submitted with the sam ple to the Laboratory. Sampler start up may be achieved by either a cold or warm s tart. Warm and cold-start optionsMATES III Final Report

Appendix III-7 as well as all other operational specifications are discussed in XonTech, Inc. Model 920 Toxic Air Sampler Operations Manual 4

.

2.3.3 ATEC 800 Sequential Sampler

2.3.3.1 Description

An ATEC Model 800 sequential sampling instrument wi ll be used to perform 6 or 8 hour integrated carbonyl sampling. The ATEC 800 in strument contains multiple channels that can be independently programmed for s pecific flowrates. Channel 1 is a multi-port channel containing eight ports. Each port can be programmed to sample over a specific time period. Optional Channels 2 a nd 3 consist of single ports that can be activated for parallel or different time per iods than Channel 1. The Xontec 920/924 samples carbonyl compounds for an integrate d 24-hour period only.

2.3.3.2 Operation

The sampler can be operated in either program or ru n modes, depending on the position of the program/run switch on the front pan el. In program mode, all of the front panel function keys can be used to program op eration cycles, display or print data, perform manual operations, set the MFC flowra te, or change the date and time. In the run mode, the sampler is activated according to the cycle programmed. If a sample is being collected, the sampler will display the current data for the active port or channel. For a full explanation of ATEC 800 ope rational procedures, refer to Models 800 and 1600 Automated Samplers Operations a nd Maintenance Manual 5

. Following sampling, the operator will remove the ca rtridges from the sampler, place them in a sealed container, and chill them in prepa ration for transport back to the Laboratory for analysis. The operator will record all appropriate data on the sample log. Note; if a power failure should occur during port sampling, the data collected for that port before the power failure will be lost . The sampler will resume operation at whatever port is active at the time power is res tored.

4 XonTech, Inc. (1987). Model 920 Toxic Air Sampler Operations Manual . Van Nuys, CA: Author.

5 ATEC. (1996). Models 800 and 1600 Automated Samplers Operations a nd Maintenance Manual. Calabasas, CA: Author.MATES III Final Report

Appendix III-8 2.3.4 MET One SASS

2.3.4.1 Description

The MET One Speciation Air Sampling System (SASS) a ccommodates up to five sampling canisters to hold multiple 47 millimeter f ilters to capture PM 2.5 particles.

The PM 2.5 separation is produced by a sharp cut cyclone (SCC ) that removes both solid and liquid coarse particles. Particle penetr ation through the SCC mimics the

PM 2.5 cutoff curve of the WINS impactor as defined by the U.S. Environmental Protection Agency. All routine maintenance can be done in the field. Filter containers are transported to the Laboratory for in spection, cleaning and changing of sampling substrates. Every element of the sampler that is contacted by the sampled air stream ahead of the filter, including the inlet can be cleaned with each sample change. The SASS was designed with individual shar p cut cyclone inlets. Particles larger than 2.5 micron aerodynamic diameter are rem oved by the cyclonic inlet

mounted with each filter container. The filter con tainers may be equipped with a

diffusion denuder ahead of the filter to remove sel ected gaseous compounds. 6

.

2.3.4.2 Module and Media Description

The integrated SASS canister contains the following components: a sharp cut cyclone, a denuder to remove nitric acid or ammonia gases, a 47 mm front filter for particle capture, a 47 mm tandem or back up filter as needed, and a cover to protect the components.

Several types of filter media are needed for assayi ng the different chemical constituents of ambient particles. The filter medi a must be suitable for the type of analysis to be done. For example, Teflon f ilters are used for gravimetric mass and trace metal determinations. Q uartz fiber filters are used for elemental and organic carbon analysis as well a s anions and cations analysis.

2.3.5 Gill Solent 2 Axis Ultrasonic Anemometer

2.3.5.1 Description

The Gill 2 Axle Ultrasonic Anemometer is used to me asure wind speed and direction (WSD) data. The performance specifications of this anemometer are delineated in Table 2-1. Data is stored in a data logger until i t is telemetered to the AQMD’s information system.

6 MET One Instruments, Inc. (2001), Model SASS & SuperSASS PM 2.5 Ambient Chemical Speciation Samplers , Grants Pass, Oregon: Author.MATES III Final Report

Appendix III-9 The wind-observer, ultrasonic anemometer consists o f a sensing head with four transducers arranged in two pairs, surmounting a cy lindrical electronic base enclosure. The onboard electronics provide all ult rasonic processing and vector computation required to output wind data in digital and analog form. For a complete description of anemometer operations, refer to Solent 2 Axis Ultrasonic Anemometer (Heated & NonHeated) User Manual and Product Specif ication 7

.

TABLE 2-1 Performance Specifications - Gill Solent 2 Axis Ult rasonic Anemometer

Wind Speed Wind Direction

1. Starting Threshold 0 mph 0 degrees

2. Range 0-145 mph 0-360\540 degrees

3. Accuracy ± 5% rms ±4 degrees

2.3.5.2 Siting

WSD measurement, barometric pressure, relative humi dity, and temperature monitoring equipment is housed in monitoring statio ns located in buildings or mobile monitoring platforms. The stations meet Env ironmental Protection Agency (EPA) criteria for National Air Monitoring Stations (NAMS) and State and Local Air Monitoring Stations (SLAMS) as cited in part 40 Cod e of Federal Register (CFR) Part 58 attached and included herein by reference.

If the meteorological equipment is located in a one -story building, it is installed on a 6.1-meter tower in an unobstructed position. If th e equipment is installed in a platform, it is mounted on a 6.1-meter mast. In th ose cases involving buildings higher than one story, the mast is made sufficientl y high to rise above the surrounding geography.

2.3.5.3 Installation

WSD equipment is assembled and oriented according t o the manufacturer's

instructions. The manufacturer’s manuals are used as the primary installation guide.

The mast base support is hinged to allow quick rais ing of the tower. The base will be welded to the top of the platform or secured to a cement base when positioned on a building. If the tower is erected close to an ex isting building, it will be secured to that building by an L-bracket. If the mast is moun ted on the housing roof, guy wires will secure it. Tower vertical alignment may be ch ecked during this process using a bubble level. If the tower is out of vertical alig nment, shimming and the use of

7 Gill Instruments, Ltd. Solent 2 Axis Ultrasonic Anemometer (Heated & Non-H eated) User Manual and Product Specification (Doc No 1172 - 0003 - lss3). Lymington, Hampshire, England: Author.MATES III Final Report

Appendix III-10 turnbuckles may be necessary. When the tripod is s ecured, the mast is fully extended with the sensor orientated in the generally correct direction. Additional guy wires

further secure the tower.

Once the WSD monitoring equipment has been assemble d, mounted on the mast, and raised to its full height in the correct orient ation, the direction sensor will be aligned to true north using a true-north-calibrated compass. Although alignment must be performed from a distance, accuracy within five degrees is possible.

2.3.5.4 Telemetry Interfacing

A telemetry system is used at existing AQMD sites w here such capabilities now exist. This system transfers WSD data from the sta tion to the AQMD central computer. The telemetry system accepts direct curr ent (DC) voltage signals from 0

to 5 volts. Since sensors other than WSD are not D C compatible, they must be converted to 0 to 5 volts DC. To convert to DC, in put the barometric pressure, temperature, and humidity sensor outputs through th e converter box that changes the sensor output to the proper voltage. The converter box consists basically of ± 15 and ± 5-volt DC power supply and an alternating current (AC) to DC converter. The input to the converter box comes directly from the sensors.

2.3.5.5 Routine Servicing

The air quality instrument specialist responsible f or each monitoring site will perform routine servicing and periodic checks of th e WSD system, barometric pressure, and temperature. The instrument speciali st must note and initial the type of service performed and the results of each periodic check on the strip chart, in the system’s daily log, and on the WSD Monthly Quality Control Maintenance Sheet (Appendix D).

Any suspected operational problem must be communica ted in detail by the instrument specialist to the appropriate supervisor . The supervisor, when informed of the problem, will contact the station operator t o determine if the problem can be corrected in-house. If the problem cannot be corre cted in-house (by the station operator), the AQMD supervisor will arrange for a s ystem repair team. Anemometer servicing will be conducted on daily, weekly, and m onthly basis as described below.

A) Daily Checks (where chart recorder is used) Each day a site is visited, the station operator wi ll write the date, station designation, comments, and initials on the strip chart. The ope rator will also provide a distinct

and accurate time check on the chart. If the time is off, the operator must provide time checks both before and after adjusting the str ip chart.MATES III Final Report

Appendix III-11 B) Weekly Checks The sonic anemometer, barometric pressure, and temp erature will be checked for daily trends as an indication of proper operation.

C) Monthly Checks

The sonic anemometer will be lowered from the tower and the transducers will be cleaned with a dry towel and water when necessary. The mounting of all three sensors will be checked to verify they are securely attached. The WSD sensor will be aligned with true north.

2.3.5.6 Diagnostics

The Gill 2 Axle Ultrasonic Anemometer microprocesso r-based system is designed with continuous internal diagnostics. These diagno stics are used to ensure that the unit is operating correctly within calibration and without potential problems. In the unlikely event of a problem with the anemometer, or if anything physically obstructs its ultrasonic pulses, the anemometer will display different status codes. The transducers will not display inaccurate data. Thir teen different status codes may

result. These codes are:

Status code 00 - System is okay Status code 01 - Transducer pair 1 failed Status code 02 - Transducer pair 2 failed Status code 04 - Transducer pairs 1 and 2 failed

Status code 08 - Non-volatile checksum error Status code 09 - Volatile memory checksum error Status code 10 - System gain at maximum Status code 50 - Marginal system gain condition Status code 51 - Measurement average building Status code 60 - Heating operational Status code 61 - Heating operational but under powe r Status code 62 - Heating tripped Status code 63 - Temperature sensor fault Status code 64 - Heating operational but over power

A status code will result when an object partially blocks the transducer pulse or the transducer begins to lose efficiency. WSD transduc ers normally receive pulses from each other within a specific range of intensity amp lified and fed to the receiving and recording electronics. When the intensity is lower than normal, the transducer will display the status code 10 as a percentage output. A status code 10 is normal ly reported just before transducer failure. The ampli fier gain is automatically increased to keep the system stable and maintain transducer a ccuracy.MATES III Final Report

Appendix III-12 Transducers have stainless steel bodies capable of handling a harsh marine environment. They are manufactured to meet Nationa l Equipment Manufacturer’s Association (NEMA) 4X or IP 65 Standards and are pr etested in a wind tunnel.

The unit, consisting of a transducer and electronic s, continuously checks itself, the transducers, and the calibration integrity and desc ribes random access memory (RAM) faults. During each measurement cycle, the u nit will perform 39 WSD measurements every second. This data is averaged a nd output one to four times per

second.

2.3.5.7 Calibration

The calibration process is completely computer cont rolled. However, operator intervention is necessary to change the erasable pr ompt chip (EPROM) found in the anemometer. An anemometer undergoing calibration i s initially fitted with special firmware that operates within reciprocal tables and transducer delays stored in RAM rather than EPROM as is customary. The first requi rement is to input the two axis path lengths and the wind tunnel temperature requir ements. At this point, the wind tunnel is switched off and the air is still. Recip rocal tables are produced for each axis based upon the path lengths entered and transm itted to the anemometer. The wind tunnel is operated up to a speed of 40 knots a nd the anemometer is rotated through 360 degrees at 5-degree steps. The perceiv ed WSD is recorded for 5 seconds at each step and the results are averaged a nd stored.

Because the unit has no moving parts, calibration a nd accuracy will not drift. The

unit has been designed to announce calibration corruptio n. Anemometer calibration can be tested by inputting a zero value for the WSD and checking the outputs or by using a calibrated fan. The unit should only be pl aced in a chamber that does not reflect ultra-sonic pulses. The only way the unit can lose its calibrations is if the distance between the traducers (path length) is alt ered. The path length can only be altered if the stainless steel arm is bent or physi cally damaged. To verify path length accuracy, the path length is measured and checked a gainst the original calibration.MATES III Final Report

Appendix III-13 2.3.5.8 Data Handling

All data generated from the WSD system will be reco rded. Specifically, the station name or number, time and date of the data run, and a brief discussion of any maintenance or repair work required will be noted o n the strip chart each day the station is visited. The wind charts may not be cut at any time. When the wind chart

is removed from the recorder and the data is reduce d, the time and date of chart removal, the station location, and the station repo rter's signature must be noted on the bottom of the printed side of the strip chart. The expended chart will be returned

to the box in which it was received. The station n ame or number and the dates of the strip chart will be noted on the end flap of the bo x. Completed Wind Data Summary Sheets and strip charts will be submitted to the Pr incipal Air Quality Instrument Specialist responsible for the station.

2.3.6 Graseby-GMW 1200 PM 10 Sampler

2.3.6.1 Description

A cross-sectional drawing of the Graseby-GMW Model 1200 two-stage, sizeselective inlet (SSI) head is shown in Figure 2-1. This sampler is used to sample particulate with an aerodynamic diameter of 10 micr ons and less. The inlet head is symmetrical and therefore insensitive to wind direc tion and relatively insensitive to wind speed. The air is drawn through the accelerat ion nozzles at 40 cfm. Particles larger than 10 microns (aerodynamic diameter) canno t follow the air stream and are

deflected below the nozzles onto the flat surface. The air sample is then drawn through vent tubes, the second-stage fractionator, and the filter where the particulate matter is collected. The height of the vent-tube i nlets above the acceleration nozzle plate prevents re-entrainment of particles.

The PM 10 sampler draws air into a specially shaped inlet at a flowrate of 40, ±4, cubic feet per minute (cfm). PM 10 particulate matter collects on an 8 x 10 inch matted quartz fiber filter surface. The concentrat ion of PM 10 particulate matter (in micrograms per cubic meter) is calculated by weighi ng the particulates collected on the filter and dividing by the measured air sample volume. The standard sampling frequency is every sixth day.

To initiate sampler start-up, the operator will com plete a PM 10 sampler site report and send it to the appropriate AQMD supervisor for review of compliance with SLAMS total suspended particulates (TSP) siting cri teria 40 CFR Part 58, Appendix E included herein by reference. The PM 10 sampler may be calibrated according to Appendix A, Section A.5.9 of the AQMD’s Quality Assurance Plan for Air Monitoring 8

.

8 Applied Science & Technology. (1996). Quality Assurance Plan For Air Monitoring. Diamond Bar, CA: South Coast Air Quality Management District.MATES III Final Report

Appendix III-14 The matted, quartz-fiber filter is very delicate an d can be easily torn or gouged. Because a damaged filter will be invalid or invalid ate results, it is important to carefully handle it by the edges. To avoid electri cal shock, the 115V AC power should be disconnected before working on the motor. Complete operational details

are contained in Instruction and Operation Manual High Volume PM 10 Sampler

9

.

FIGURE 2-1 Graseby-GMW PM 10 Sampler, Model 1200 with Two-Stage, SSI Head

9 Graseby Anderson. (1988). Instruction and Operation Manual High Volume PM 10 Sampler. Atlanta,

GA: Author.MATES III Final Report

Appendix III-15 Chapter 3.0 Laboratory Procedures

3.1 INTRODUCTION

Since 1994, the AQMD has implemented the U.S. EPA P AMS program to gather data on ozone precursors. Some of the same sampling instrum ents currently used in the PAMS program may be used in the MATES III and microscale efforts. Hence, many of the procedures and protocols for the MATES III program will be taken from the AQMD Quality Assurance Plan for Air Monitoring 10 (updated July 1997). However, MATES III also utilizes several analytical methods not perfor med in the PAMS program and the protocols include herein will parallel accepted ARB and EPA procedures.

The AQMD will rely upon Air Quality Instrument Spec ialists to take the field samples and deliver them to the Laboratory sample custodian . The Laboratory sample custodian will handle logging and distribution within the AQM D. Procedures for proper sampling and initial chain-of-custody are outlined in the AQ MD PAMS Air Monitoring Network Quality Assurance Plan 11 , Section 7E Parts 1 and 2.

3.2 SAMPLE HANDLING

All sampling media will be handled according to the Laboratory practice for implementation of toxics analysis and particulate m atter network programs as applicable. Field instrument specialists will complete the samp ling information and chain-of-custody

forms 12 , and deliver the samples to the Laboratory sample custodian.

3.2.1 Canister Cleaning

The AQMD Laboratory has a canister cleaning oven sy stem. This system utilizes humidified nitrogen to flush and clean canisters in a heated oven to less than 5-ppb carbon of total organic compounds. The canisters a re held at a 80 o C temperature and are flushed a minimum of seven times over a 2 1⁄2 -hour p eriod. Every canister is removed from the canister cleaning oven and analyzed for re sidual hydrocarbons. Long-term experience has proven that the canister-cleaning ov en system is sufficient to provide clean canisters. Any hydrocarbons (above the threshold c oncentrations) found in the checked canister are cause for investigation and corrective action. The cleaning date and operator are noted on the canister tag and in an electronic database that serves as the primary chain-of-custody.

10 Applied Science & Technology. (1996). Quality Assurance Plan For Air Monitoring. Diamond Bar, CA: South Coast Air Quality Management District.

11 Applied Science & Technology. (1977) PAMS Air Monitoring Network Quality Assurance Plan. Diamond Bar, CA: South Coast Air Quality Management District.

12 These forms consist of the Size-Selective Inlet PM 10 Sampler Envelope (Appendix C), MATES II Sample Log (Appendix F), and VOC Canister Tag (Appendix G)

.MATES III Final Report

Appendix III-16 3.2.2 Field Canister Use

The canisters are transported by the instrument spe cialist to the site and installed in accordance with the sampling SOP included in the PAMS Air Monitoring Network Quality Assurance Plan 13 . The sample is taken and the sample time, caniste r number, and start and stop vacuum are noted on the MATES III Sample Log (Appendix F) that

follows the canister from the field onward. The sa mple is promptly returned to the Laboratory for log-in and distribution to the appro priate Senior Chemist.

3.2.3 Sample Distribution in the Laboratory

The Laboratory sample custodian (Senior Chemist) wi ll log in the samples received from the courier and distribute them to the appropriate Chemist following established Laboratory protocol. The sample custodian will dis tribute samples to the Laboratory personnel starting with the responsible Senior Chem ist.

3.3 ANALYSIS METHODS

Table 1 gaseous compounds (Appendix A) will be anal yzed using gas chromatography with multiple detection for the gaseous compounds. The method generally follows the EPA Method TO-15; Determination of Volatile Organic Compounds (VOCs) in Specially Prepared Canisters and Analyzed by Gas Chromatograp hy/Mass Spectrometry (GC/MS)

. Carbonyl analysis will be conducted using EPA Metho d TO-11, Determination of Formaldehyde in Ambient Air Using Adsorbent Cartrid ge Followed by High Pressure Liquid Chromatography . These methods are detailed in the EPA Compendium of Methods for the Determination of Toxic Organic Comp ounds 14

.

13 Ibid.

14 Winberry, William, Murphy, Norma & Riggan, R.M. ( 1988). Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air. Research Triangle Park, NC: Quality Assurance Division, Environmental Monitoring System s Laboratory, Office of Research and Development, US Environmental Protection Agency. (EPA-600/4-84- 041)MATES III Final Report

Appendix III-17 3.4 SAMPLING AND ANALYSIS - TABLE 1 COMPOUNDS

The VOCs and halogenated VOCs found in Table 1 (App endix A) will be analyzed by cryogenic freeze-out to obtain the lowest possible detection limits. These compounds will be detected using a combination of gas chromat ography with mass spectrometry and flame ionization detection. A short method descrip tion for sampling and analysis of VOCs by GC/MS can be found in this document as Appe ndix M.

Carbonyl measurement will be conducted utilizing th e PAMS sampling and analysis methodology delineated in the PAMS Air Monitoring Network Quality Assurance Plan 15

. The Waters ® silica gel cartridge impregnated with dinitropheny l hydrazine will be used to sample for carbonyl compounds. A potassium-iodi de-coated ozone denuder will be used in all carbonyl samplers. The California Air Resources Board (CARB) toxic network design method will be followed using the Xo nTech 920/924 with a carbonyl channel. A short method description for the carbon yl sampling and analysis can be found in this document as Appendix H. The ATEC Model 800 sampler will be used for sampling at the microscale sites. This model is si milar to the AQMD’s PAMS sampler.

Inorganic measurements will be taken on Teflon filt ers using XonTech 920/924 samplers and analyzed by Energy Dispersive X-ray fluorescenc e (EDXRF). For the PM 2.5 samples, a Teflon filter will be used, and EDXRF will be use d for analysis of elemental constituents. A short method description for sampl ing and analysis of elements by energy dispersive X-ray fluorescence spectrometry is attac hed to this document as Appendix J.

Proposed for particulate filter samples both in the coarse (PM 10 ) and fine (PM 2.5 ) aerodynamic diameter regions will be analyzed for m etals, ions, total mass, OC, EC, and total carbon (TC). The protocol for mass and ions will follow the same methodology as used in the AQMD (federally recognized) PM 10 Network. Analysis for EC, OC and TC upon the PM 10 filter samples will be analyzed using the Interagen cy Monitoring of Protected Visual Environments (IMPROVE) method with some overlapping National Institute of Occupational Safety and Health (NIOSH) Method 5040 analysis. Analysis for EC, OC and TC upon the PM 2.5 filter samples will be analyzed using the IMPROVE method with some overlapping NIOSH analyses. Both methods similarly evolve carbon from the filters by heating but differ operationall y in their temperature and optical monitoring protocols. The results of the overlappi ng analyses between the NIOSH and IMPROVE methods will be compared. The results from the IMPROVE and NIOSH methods are expected to not be directly comparable, a factor may be realized which will allow for a comparison of the future NIOSH data wit h AQMD’s historical PM database consisting of data measured by the IMPROVE method. Furthermore, seasonal and annual trend analysis will be conducted on data acquired f rom air monitoring stations used in

both MATES II and MATES III.

15 Applied Science & Technology. (1977) PAMS Air Monitoring Network Quality Assurance Plan. Diamond Bar, CA: South Coast Air Quality Management District.MATES III Final Report

Appendix III-18 The preceding discussion covers all Table 1 compoun ds (Appendix A) that will be sampled on a regular, one-day-in-three sampling sch edule synchronized with the national

PM 10 and PM 2.5 network schedules. The samples will be integrated over a 24-hour period. AQMD personnel will conduct the sampling a nd analysis. Hired contract Instrument Technicians and Chemists will assist reg ular AQMD employees.

3.5 SAMPLING AND ANALYSIS - TABLE 2 COMPOUNDS

Although many Table 2 compounds (Appendix B) do not have a widely recognized analytical method, every effort will be made to fol low American Society of Test Methods or American Industrial Hygiene Laboratory methodologies. The compounds ethylene dibromide and ethylene dichloride can be seen on ch romatograms of the halogenated hydrocarbons analyzed for Table 1 compounds. Since these compounds are rarely used in the Basin, they are on the Table 2 list because the y will be evaluated on an infrequent

basis.

Compounds found in Table 2 are difficult to measure . Some Table 2 compounds may be sampled by the AQMD and analyzed by external labora tories. Special efforts may be directed to analyzing the ambient air for naphthale ne, one of the PAHs.

3.6 SAMPLING SCHEDULE

MATES III sampling will be conducted on the same sc hedule as utilized by the airmonitoring network. The air monitoring network sam pling schedule can be found on the U.S. EPA website at; www.epa.gov/tnn/amtic , and is for the six-day and three-day monitoring schedule for TSP, Pb, PM 10 , PM 2.5 and VOC. Using the same sampling

schedule results in several benefits:

1) Data from MATES III can be correlated with the ambi ent data taken on the same day. 2) Additional staff time to service and maintain MATES III sampling equipment

and instrumentation is minimized because the existi ng sampling schedule can be largely utilized. 3) Sample set-up, retrieval, and delivery time to the Laboratory is minimized.MATES III Final Report

Appendix III-19 Microscale site sampling shall be conducted on a si milar schedule to MATES III sampling. The AQMD will operate two to three micro scale site sampling platforms. Platforms will be sited for eight weeks at each of a variety of different locations. Sampling will occur on days the MATES III fixed sit es are sampling. The schedule for microscale site sampling is depicted in Table 3-1. Sampling at the microscale sites will coincide with the MATES III sampling schedule (that is on a one-day-in-three schedule for approximately six weeks.

Table 3-1 Sample Mobile Platform Sampling Schedule

Mon Tues Wed Thurs Fri Sat Sun

Week 1 X X X

Week 2 X X

Week 3 X X

Week 4 X X X

Week 5 X X

Week 6 X XMATES III Final Report

Appendix III-20 Chapter 4 Quality Assurance and Quality Control

4.1 INTRODUCTION

To achieve the highest possible data quality level in the MATES III, the AQMD has implemented the following Quality Assurance/Quality Control (QA/QC) plan. This Chapter contains the objectives, procedures, documentation, and data review techniques that will be used by the AQMD to assure that the MATES III will produ ce accurate data.

4.2 OBJECTIVES

There are three objectives of the QA/QC procedures for the MATES III. These objectives are: (1) to provide accurate and precise data to meet AQ MD monitoring requirements; (2) to minimize data loss; and (3) to assess air monitorin g data quality and provide data that meets the QA/QC data quality objectives displayed in Table 4- 1.

TABLE 4-1 QA/QC Data Quality Objectives

CRITERIA/PARAMETER

ASSESSMENT MEASURES PROCEDURE VOCs Carbonyls PM 10 PM 2.5 Accuracy Percent Deviation from

True Value Audits ± 25% ± 25 % ± 10% ± 10%

95% Probability Limits < 30% < 30% < 15% < 15%

Precision Percent Deviation from

True Value Collocation ± 25% ± 25% < 10% < 10%

95% Probability Limits < 30% < 30% < 15 % < 15 % Completeness Percent of Valid Data 85% 75% 90% 90%

4.3 PROCEDURES

4.3.1 Quality Assurance Procedures

The AQMD will perform annual flow audits on all PM 10 and PM 2.5 samplers. These flow audits will be conducted according to the procedures outli ned in the AQMD’s Quality Assurance Plan for Ambient Monitoring , Appendix K. In addition the California Air Resou rces Board (CARB) performs quarterly audits of flows at District air monitoring stations. The CARB also annually audits laboratory systems related to mass measureme nt in the PM 2.5 and PM 10 networks. The EPA and CARB will annually audit the performance of the AQMD Laboratory for VOCs, carbonyls and lead (Pb) using the EPA’s National Pe rformance Audit Program and the CARB’s toxic VOC performance audit.

Resources permitting, the AQMD will operate a Xonte c 920 for collocated measurement of metals, hexchrome and carbonyls at the Rubidoux fix ed site. The AQMD will operate collocated

Hi-Vol PM 10 samplers at Rubidoux for a 24-hour average. The c ollocated samplers will operateMATES III Final Report

Appendix III-21 on a one-day-in-six sampling schedule. VOC samplin g will be collocated at Pico Rivera on a one-day-in-three sampling schedule.

The AQMD will endeavor to enlist outside laboratori es to analyze a small number of split samples for a majority of the compounds measured. The ARB has the capability of performing system audits of the AQMD Laboratory, through the p robe toxics audits, whole air samples (round robins) and will be the primary outside audi tor of the program.

4.3.2 Quality Control Procedures

A) Field Checks

AQMD staff will perform a number of functions when conducting a field check. Specifically,

staff will:

1) observe and record all required data for each sampl er’s monthly maintenance sheet, chainof-custody form, and sample identification tag 2) check and reset all timers if off by more than ± 5 minutes Local Standard Time 3) check and adjust the flow settings if they are not within ± 5% of the calibrated setting

B) Laboratory Daily Checks

AQMD staff will monitor the balance using a NIST tr aceable check standard; conduct a gas chromatograph standard check using a NIST traceable gas standard; will observe, record, and correct all sample media equilibration conditions i f they are out of tolerance.

C) Semi-Annual Checks

AQMD staff will conduct multipoint calibrations of all mass-flow controllers in all samplers; perform instrument leak checks; determine the level of detection (LOD) for each analytical method; and will clean the PM 10 inlet head.

D) Annual Checks

AQMD staff will clean the sample probe using de-ion ized water and a soft cloth; conduct sample probe leak checks and repair if necessary; and will conduct 24-hour tests by operating the sampler with a daytime start-stop time to observe a ctual run length. Actual start and stop must be observed. The timer will be repaired if the sam ple period varies from setting by more than ±

20 minutes.MATES III Final Report

Appendix III-22 4.4 DOCUMENTATION

A critical element of an effective QA/QC system is proper documentation. To ensure that all samples are properly handled, inspected, collected, analyzed, and reported, a comprehensive set of QA/QC documents will be completed. The information repor ted in these documents is crucial to determining the validity of reported data. Lack of proper documentation can be grounds for data invalidation. A summary of QA/QC sampling act ivities is attached as Appendix L.

A) Chain-of-Custody Forms

Chain-of-custody forms (Appendices C, F, F-1 and G) are necessary to identify and control the disposition of the samples through the multiple ste ps of preparation, sampling, retrieval, analysis, and data reporting. As appropriate, by sample type , chain-of-custody forms will accompany all samples collected in the MATES III and MSS Programs . These forms will be originated by the field operators, delivered to the Laboratory, and s ubmitted to the assigned Laboratory staff. The Laboratory will be responsible for storing all chai n-of-custody documents.

B) Maintenance Check Sheets

Maintenance check sheets (Appendices D and E) will be completed by field instrument operators

for the PM 10 sampler and ultrasonic wind speed and direction an emometer. These monthly

maintenance sheets will be submitted to senior fiel d operators for review, approval, and storage.

C) Calibration Reports

Field and Laboratory staff performing semi-annual a nd post-repair multipoint calibrations will prepare calibration reports. The calibration repor ts will be reviewed, approved, and retained by field and Laboratory staff.

D) Equipment Relocation Notes (ERN)

ERNs are an element of the documentation required i n MATES III. Because the microscale monitoring element involves frequent relocation of equipment, it is the responsibility of the field operations supervisor or repair supervisor to note in the station logbooks for each instrument the location and time period the instrument was in serv ice.

E) Station and Equipment Logbooks

Logbooks are provided for each sampling site and pi ece of sampling equipment. Each and every monitoring station visitor will note the station lo gbook at each and every visit. The notation should include the date, reason for the visit, and the visitor’s clearly identifiable signature or initials. Instrument logbooks will be noted each t ime an instrument is repaired, calibrated, or

audited.MATES III Final Report

Appendix III-23 4.5 DATA REVIEW

Program data validity is directly attributable to t he proper implementation of all the operating and QA/QC procedures described in this protocol. To as sure that the program’s data quality objectives are met, responsibility for data review is distributed between the field operators, calibrators, auditors, and supervisors, Laboratory Chemists and Supervisors, QA Supervisors, and the Laboratory and Air Monitoring Managers.

A) Field Supervisors

Field supervisors are responsible for locating and setting up the sites, scheduling operators, training field operators, coordinating supply order ing, supply receipt and distribution, and review of monthly QC maintenance sheets. The field superv isors are responsible for notifying the Laboratory supervisor of every event that could inv alidate the sample.

B) Field Operators

Field operators are responsible for operating all s amplers and analyzers according to the operating procedures specified in this protocol. T he field operators must observe and annotate all information in the monthly QC maintenance sheets, c hain-of-custody forms, sample tags, and logbooks. The field operators are responsible for notifying their supervisors of every out-ofcontrol flow setting, timer setting, expected start or ending pressure, or any other instrument

malfunction.

C) Field Calibrators

Field calibrators are responsible for performing se miannual multipoint calibrations on all flow control-devices according to AQMD calibration proce dures. Any as-is calibration showing a deviation from design flowrate in excess of ± 15% will be reported to the field supervisor. Any samples collected while flow percentage deviation f rom design flow exceeded ± 15% will be invalidated back to the previous flow calibration, audit, or malfunction date.

D) Field Auditors

AQMD field auditors will conduct flow audits on 25 percent of the entire network each calendar quarter. Auditors are responsible for notifying th e QA supervisor of any audit indicating a greater than ± 15% average percent deviation from design flow.

E) QA Supervisor

The QA Supervisor is responsible for reviewing fiel d audit reports, scheduling audits, coordinating with ARB QA staff, and compiling and r eporting QA flow accuracy reports.MATES III Final Report

Appendix III-24 F) Laboratory Chemists

The Laboratory Chemists are responsible for receivi ng field samples, maintaining and storing chain-of-custody documents, performing and document ing QC activities on the QC monthly maintenance sheets, performing Laboratory audit ana lyses, and conducting preliminary data analysis for outliers and out-of-control conditions

.

G) Laboratory Supervisor

The Laboratory Supervisor is responsible for final raw data review; calculation of precision based upon collocated sampling; reviewing monthly QA/QC s heets; making final evaluation of data validity based on satisfactory reports from QA supe rvisor and field supervisor; and assessment of Laboratory precision data.

H) Air Monitoring Manager

The Air-Monitoring Manager is responsible for overs eeing field operations and QA auditing operations.

I) Laboratory Manager

The Laboratory Manager is responsible for overall c oordination of MATES III and for ensuring that all staff fulfills their responsibilities as d etailed in this protocol. Additionally, the Laboratory Manager is responsible for establishing the final acceptance criteria for sample validity once actual precision and accuracy data be come available.MATES III Final Report

Appendix III-25 Chapter 5.0 Data Processing and Reporting

5.1 INTRODUCTION

MATES III monitoring for ambient air toxics will de velop a large data resource for future analysis. Table 1 compounds, when multiplied by th e projected frequency of sampling in MATES III, will result in more than 20,000 individu al data points representing a concentration of a toxic compound at a particular time and location. The purpose of this chapter is to outline the data handling of such a large database. This secti on will only pertain to the laboratory work performed and not to the meteorological, criteria p ollutant, or monitor calibration data.

The AQMD Laboratory has had prior experience handli ng such a large data base as part of MATES II. Reporting templates for the carbon analy sis and XRF elemental analysis (inorganics) will follow the outline used in MATES II. Reportin g templates for the VOCs, halogenated hydrocarbons, and carbonyls will follow the PAMS fo rmat.

The aim of the reporting will be to generate Excel data files for electronic transfer to interested parties. The data will be checked for transcriptio n errors and quality assured to represent the most accurate determinations possible. The Laborat ory will strive to disseminate the data in a timely fashion to facilitate feedback.

5.2 DATA BASE COMPILATION

The Laboratory Chemists will generate a data point representing the concentration of a particular compound found over a particular time period at a p articular site. The instrument analyzes the sample and determines the volume concentration on a parts-per-billion basis. These concentration numbers will be compiled into a sprea dsheet along with the name of the sampling site and the date the sample was taken. The Chemis t (analyst) is responsible for checking data point accuracy. The technician in charge of copyin g the data points into the spread sheet is responsible for their accurate transcription. The Senior Chemist is in charge of double checking the Chemists’ and technicians’ data transcription w ork.

If resources permit, one Chemist will operate the i nstrument while another Chemist reduces the data and transcribes it to the Excel spreadsheet. This method would lead to the quickest turnaround time possible. One Chemist may reduce t he data from several instruments depending

on the workload.

MATES III data will encompass PM 10 and PM 2.5 mass, ions for both fractions, VOCs, carbonyls, XRF, ICP/MS and carbon analysis results. The run d ate will be encoded with the year, month, and day in six numerals. This information will be followed by a two-letter acronym representing

the station and concentration. The column header h as the name of the compound and the concentration units. Uncertainties were given for each data point. These uncertainties encompass the calculated limits for the sampling an d analysis errors introduced into the
measurement system.MATES III Final Report

Appendix III-26 The MATES III data will be compiled into several sp readsheets. These spreadsheets will conjugate components along the lines of the analysi s technique. Each instrument will have a separate spreadsheet for the compounds it analyzes.

The Laboratory can work with the end data user to s upply the electronic version in whatever file length or configuration is desired. The data can a lso be translated into ASCII flat files.

5.3 PERIODIC REPORTS

The Laboratory will strive to meet a two-month turn around time from the date of sampling to the finished and checked report. The VOCs, carbonyls, XRF, and carbon analyzer will all be sampled individually, yet in very similar formats. Extra effort will be made to analyze duplicate samples and other QC samples and compile into a sep arate report for monthly reporting. The reports will be available in electronic file and pr inted spreadsheets.

5.4 FINAL REPORT

Past experience has proven that the final report in cluding the QA report can take from four to six months after the last day of sampling to complete. The data will be compiled on a monthly basis, and the final report is slated to be complete withi n two months of the end of sampling. Resources permitting, Laboratory staff will migrate the Excel spreadsheets to the Access database software. The final report will be stored in several files segregated by date and analysis. The AQMD Laboratory has the ability to write the fi les to CD-ROM. Only limited hard copies of the report will be printed.MATES III Final Report

Appendix III-27 Glossary

Quality Assurance (QA) The practice of establishing procedures external t o the day-to-day monitoring operations that indicate whether or not air quality data is accurat e, representative, precise and complete enough to satisfy the needs of the data users. QA activit ies include, but are not limited to, system and performance audits and collocated and parallel samp ling. These activities are described in detail in Chapter 4.

Quality Control (QC) Any procedure incorporated into the internal, day- to-day operations of collection and analysis of air quality samples to satisfy the data user’s need for valid data. These activities are described in detail in Chapter 4.

Accuracy A determination of how closely reported data values are to true values. Annually conducted performance audits will challenge the various sampl ers and instruments used in this program to assess their accuracy. All program data accepted a s valid will meet the criteria set forth in Table 4-1. Accuracy is expressed as “percent” deviation from true and is calculated as follows:

Percent Deviation from

True = Indicated Value - True Value

True Value x 100

Precision The measure of monitoring system repeatability. Pr ecision is determined by amassing a variety of measurements of the same true value over a perio d of time and assessing the variability of those measurements. Precision objectives for the v arious monitoring methods used in MATES II and MSS programs are presented in Table 4-1.

Data Completeness (DC) The percent of valid data points actually collecte d out of the total number of data points possible. The data completeness objectives for the MATES II a nd MSS programs are presented in Table 4- 1. DC is calculated using the following formula:

percent DC = Total valid data points Total number of possible data points x 100

Representativeness The goal that samples are representative of both t emporal and/or spatial scales at all sites. This i s accomplished by conforming to 40CFR58 siting and sa mpling requirements for PM 10

.

Performance Audit A procedure conducted to establish individual anal yzer and overall sampling and analysis accuracy. Probe audits are used to measure the int egrity of both the sampling and analysisMATES III Final Report

Appendix III-28 systems. Flow audits measure the accuracy of the f low metering devices that assure the sample’s temporal representativeness. Gas standard audits d etermine accuracy of laboratory analyzers in measuring known concentrations of toxic compounds.

System Audit An on-site inspection and review of the entire moni toring program.

Collocated Sampling The process of running two identical samplers conc urrently at the same location. Collocated data measures a method’s precision. One of the samplers is designated A and is treated as the true value; while the other sampler is designated B and is regarded as the indicated value.

Parallel Sampling The process of two different agencies such as the AQMD and ARB operating two different samplers side-by-side.MATES III Final Report

Appendix III-29 ACRONYM LIST

AC alternating current AIHL American Industrial Hygiene Laboratory AM Air Monitoring AQMD South Coast Air Quality Management District

ARB Air Resources Board AST Applied Science and Technology ASTM American Society of Test Methods

Basin South Coast Air Basin

cc cubic centimeters ccm cubic centimeters per minute cfm cubic feet per minute

CFR Code of Federal Records

DC direct current DNPH 2, 4-dinitrophenyl-hydrazine EDB ethylene dibromide EDC ethylene dichloride

EJ-2 Environmental Justice Initiative Number 2 EPA Environmental Protection Agency EPROM erasable prompt chip ERN equipment relocation notice ETM elapsed time meter FPC filter paper cartridge HPLC High Performance Liquid Chromatograph ICP/MS Ion coupled Plasma/Mass Spectrometry LIMS Laboratory Information Management System

LOD Level of Detection lpm liters per minute MATES II Multiple Air Toxics Study II MATES III Multiple Air Toxics Study III

MFC mass flow controller mph miles per hour MSS Microscale Study MTBE methyl tert butyl ether NAMS National Air Monitoring Stations NEMA National Equipment Manufacturer’s Association PAH polycyclic aromatic hydrocarbon PAMS Photochemical Assessment Monitoring Station PM particulate matter ppb parts per billion ppbC parts per billion carbon PSI pounds per square inch

PST Pacific Standard Time PTEP Particulate Technical Enhancement ProgramMATES III Final Report

Appendix III-30 PUF polyurethane foam QA quality assurance QC quality control RAM random access memory

rms root mean standard SASS speciation air sampling system SCAQMD South Coast Air Quality Management District SCC sharp cut cyclone SCFM standard cubic feet per minute SLAMS State and Local Air Monitoring Stations SOP standard operating procedure

SSI size selective inlet

TAC toxic air contaminant TSP total suspended particulates

V Volt VOC volatile organic compound WSD wind speed and direction XRF X-ray fluorescenceMATES III Final Report

Appendix III-31 APPENDIX A Proposed Table 1 Air Contaminants for Inclusion in the Measurement Program (Compounds in bold are proposed for U.S EPA AIRS database reporting)

CAS No. Chemical Name Lab Test Method Sampling Freq. Comment

VOCs

71-43-2 Benzene GC/MS/FID 1 in 3 days 106-99-0 Butadiene [1,3] GC/MS/FID 1 in 3 days (o-) 95-50-1 Dichlorobenzene [ortho- & para] GC/MS/ FID 1 in 3 days 100-41-4 Ethyl Benzene GC/MS/FID 1 in 3 days 100-42-5 Styrene GC/MS/FID 1 in 3 days

108-88-3 Toluene GC/MS/FID 1 in 3 days (m-) 108-38-3 Xylene [m+p, o-] GC/MS/FID 1 in 3 days 75-01-4 Vinyl chloride GC/MS/FID 1 in 3 days

Halo-HCs

56-23-5 Carbon tetrachloride GC/MS/FID 1 in 3 days

67-66-3 Chloroform GC/MS/FID 1 in 3 days 75-09-2 Methylene chloride (Dichloromethane) GC/MS/ FID 1 in 3 days 127-18-4 Perchloroethylene (tetrachloroethene) GC/MS /FID 1 in 3 days 78-87-5 Propylene Dichloride (1,2-dichloropropane) G C/MS/FID 1 in 3 days Not in MatesII 79-01-6 Trichloroethylene GC/MS/FID 1 in 3 days Carbonyls 75-07-0 Acetaldehyde HPLC 1 in 3 days

67-64-1 Acetone HPLC / GC/MS/FID 1 in 3 days Not Reported 50-00-0 Formaldehyde HPLC 1 in 3 days 78-93-3 Methyl ethyl Ketone (MEK) HPLC/GC/MS/FID 1 i n 3 days Not Reported 1634-04-4 Methyl tert-Butyl Ether (MTBE) HPLC/GC/MS/ FID 1 in 3 days Not Reported Inorganics

7429-90-5 Aluminum ICP/MS:XRF 1 in 3 days

7440-38-2 Arsenic ICP/MS:XRF 1 in 3 days 7440-41-7 Beryllium ICP/MS:XRF 1 in 3 days

7440-43-9 Cadmium ICP/MS:XRF 1 in 3 days

7440-70-2 Calcium ICP/MS:XRF 7440-47-3 Chromium (total) ICP/MS:XRF 1 in 3 days Chromium (hexavalent) IC 1 in 3 days

7440-48-4 Cobalt ICP/MS:XRF 1 in 3 days 7440-50-8 Copper ICP/MS:XRF 1 in 3 days

7439-89-6 Iron ICP/MS:XRF 1 in 3 days

7439-92-1 Lead ICP/MS:XRF 1 in 3 days 7439-95-4 Magnesium ICP/MS:XRF 7439-96-5 Manganese ICP/MS:XRF 1 in 3 days

7440

- 02

- 0 Nickel ICP/MS:XR F 1 in 3 days

7723

- 14

- 0 Phosphorous ICP/MS:XRF 1 in 3 days

7440

- 09

- 7 Potassium ICP/MS:XRF 1 in 3 days

7782

- 49

- 2 Selenium ICP/MS:XRF 1 in 3 days CAS No. Chemical Name Lab Test Method Sampling Freq. Comment

7440-21-3 Silicon ICP/MS:XRF 1 in 3 days

7440-62-2 Vanadium ICP/MS:XRF 1 in 3 days

7440

- 66

- 6 Zinc ICP/MS:XRF 1 in 3 days
Others Elemental & organic carbon C analyzer 1 in 3 days

Criteria Pollutants

PM 2.5 SASS 1 in 3 days Speciation

PM 10 SSI

- Hivol 1 in 3 days PM networkMATES III Final Report

Appendix III-32 APPENDIX B Proposed Table 2 Air Contaminants that Potentially May Be Mo nitored on

A Limited Basis

Laboratory

CAS No. Chemical Name Test Method Comment

VOCs

Acrolein No ambient method

Halo-HCs

106934 Ethylene dibromide {EDB} GC/MS

107062 Ethylene dichloride {EDC} GC/MS

Others

PAHs HPLC Send out for analysis

Napthalene HPLC Send out for analysis

Diesel exhaust “Markers” TBD Send out for analysisMATES III Final Report

Appendix III-33 APPENDIX C Size-Selective Inlet PM 10 Sampler Envelop

South Coast Air Quality Management District Applied Science & Technology

Size-Selective Inlet PM 10 Sampler Envelop



FIELD OPERATOR USE  LABORATORY USE ONLY  

STATION #  SAMPLE # 

LOCATION  FLOWRATE, CFM 

SAMPLER #  VOLUME OF AIR, M 3 
QUARTZ 

FILTER #  FINAL WEIGHT (gm) 

DATE  TARE WEIGHT (gm) 

TIME  SAMPLE WEIGHT (gm) 

END  PM 10 ( μ g/M 3 ) 

START  SAMPLE RECV’D 

TOTAL  

REMOVED FROM SAMPLER  SAMPLE WEIGHED 
SENT TO HQ  SAMPLE EXTR. 

RECEIVED AMB  SAMPLE ANALYSIS   REF.

DATE SAMPLER CALIBRATION

STATION OPERATOR

Remarks (unusual activities sampling conditions, e tc.):MATES III Final Report

Appendix III-34 APPENDIX D WSD Monthly Quality Control Maintenance Check Sheet

SOUTH COAST AIR QUALITY MANAGEMENT DISTRICT

MONTHLY QUALITY CONTROL MAINTENANCE CHECK SHEET

MAKE/MODEL Wind Speed and Direction System

Location Month/Year

Station No. Specialist

Control No. Reviewed by Date

Zero Speed Zero Direction Visual Wind Chart Time

Date As Found Final As Found Final Transmitter Check As Found Final

OPERATOR INSTRUCTIONS:

Daily Checks: Chart trace and time. Weekly Checks: Zero speed and direction inking syst em Visual wind transmitter check. The station operato r will visually check the wind transmitter to confi rm the
direction coincides with recorder. Notify supervis or immediately if problem occurs.

Bi-monthly

Maintenance:

DATE COMMENTS OR MAINTENANCE PERFORMED

Calibration Date: OperatorMATES III Final Report

Appendix III-35 APPENDIX E High Volume Monthly Quality Control Maintenance Che ck Sheet

High Volume Monthly Quality Control Maintenance Check Sheet

MAKE/MODEL HIGH VOLUME SAMPLER

Location Month/Year Station No. Specialist Control No. Reviewed by/Date Operating Set Point Cubic Feet per Meter Date SSI Head Cleaned Due Date

Sample
Date Initial

Flow cfm Final Flow

cfm Filter

No. Initial

Elapsed Time Final

Elapsed Time Total

Time

1
2
3
4
5

6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31MATES III Final Report

Appendix III-36 APPENDIX F MATES III Sample Log



## South Coast Air Quality Management District

# 	

	



Location:

Sample Date:

Station No.:

Retrieved By:

Retrieval Date:

**Canister Log – XonTech 910** 

### Sample

Time Canister

No. Start

Vacuum End

Pressure Comments

24 hour

Blank

Collocated

**DNPH Cartridge Log – XonTech 920** 

### Sample

Time Cartridge

No. Elapsed

Time Flow Rate Comments

24 hour

Blank

Collocated

**Filter Log – XonTech 920** 

### Sample Time Filter No. Flow Rate Comments

Teflon (Metals)

Cellulose (Chrome VI)

PM 10 (Hi-Vol) 

### Lab No.:

Date Sample Received:

Reference No.:

Analyst: Lab No.:

Date Sample Received:

Reference No.:

Analyst:(Staple Printout Here)MATES III Final Report

Appendix III-37 APPENDIX F-1 MATES III Sample Log



## South Coast Air Quality Management District

# 
	


	



Location:

Sample Date:

Station No.:

Retrieved By:

Retrieval Date:

**Canister Log – XonTech 910** 

### Sample

Time Canister

No. Start

Vacuum End

Pressure Comments

24 hour

0-8 hour

8-16 hour

16-24 hour

**DNPH Cartridge Log – XonTech 920** 

### Sample

Time Cartridge

No. Elapsed

Time Flow Rate Comments

24 hour

0-8 hour

8-16 hour

16-24 hour

**Filter Log – XonTech 920** 

### Sample Time Filter No. Flow Rate Comments

Teflon (Metals)

Cellulose (Chrome VI)

PM 10 (Hi-Vol) 

### Lab No.:

Date Sample Received:

Reference No.:

Analyst: Lab No.:

Date Sample Received:

Reference No.:

Analyst:(Staple Printout Here)MATES III Final Report

Appendix III-38 APPENDIX G VOC Canister Tag

VOC CANISTER TAG

SCAQMD PAMS CAN

#

STATION LAB

Code Date Time Initial Analysis Clean

Notes

Notes

Notes

Notes

Notes

Notes

Notes

Notes

Notes

Notes

NotesMATES III Final Report

Appendix III-39 APPENDIX H Method Description for Sampling and Analysis of Car bonyls by HPLC at the AQMD Laboratory

Sampling - Ambient air is drawn through a glass and/or stai nless steel probe at the air monitoring site and pulled through DNPH coated sili ca cartridges mounted in the A-Tech 800 sampler. The sampling cartridges are coated with a minimum of 300 mg of DNPH on Waters Sep-Pak silica cartridges. The sample is pulled th rough the cartridge at approximately one lpm for 8-hour sampling and at 0.7 lpm for 24-hour samp ling. Before and after sampling the cartridges are kept capped and refrigerated in smal l vials to prevent loss and contamination.

Laboratory Analysis - The laboratory uses a Waters Millennium system hi gh performance liquid chromatograph (HPLC) with autosampler. After elution of the Sep-Pak car tridge with 3 milliliters of acetonitrile, the samples are placed in the autosampler. Samples are run isocratically (55% acetonitrile and 45 % H 2 0) on a Waters C-18, 5 micron, 4.6 mm by 250-mm column. Flow is one milliliter per minute. Twenty microliters are injected onto the column by the autosampler.

Quantification - A calibration curve is derived from multipoint in jections of standards obtained from Radian Corporation. One point control standar ds are run daily with the sample analysis. PAMS compounds, acetaldehyde, formaldehyde, and ace tone, are quantified by comparison to

the calibration curve.

QA/QC - The limit of detection is determined for the HPLC response and the system LOD is calculated for a typical air volume sampled. A col located cartridge is run every 6 days of sampling in the field. Blank cartridges are run at a similar frequency. Replicate samples are run every ten samples.MATES III Final Report

Appendix III-40 APPENDIX I Method Description for Sampling and Analysis of Ele ments by Energy Dispersive X-ray Fluorescence Spectrometry at the AQMD Laboratory

Sampling- Ambient air is drawn through a 47 mm Teflon filter loaded in a TSP or PM 2.5 sampler. Typically, 24 hour sampling at about 20 lpm provide s sufficient sample mass on the filter for a successful analysis. The sampler must collect a ho mogeneous sample across the surface of the filter. The Kevex XRF instrument examines a very s mall cross section of the filter near the

center.

Laboratory Analysis- A Kevex Energy Dispersive X-ray fluorescence spectr ometer is used to analyze 35 elements in the filter sample. There is no need for sample preparation other than bringing the filters to room conditions. Each filt er is loaded onto a sample wheel brought to a

vacuum and scanned under five different instrumenta l conditions. Each condition is optimized for certain groups of elements. After spectral acq uisition, an identification and deconvolution process extracts the net contributions of counts of each of the 35 elements.

Speciation and Quantification- Each element has a unique spectral pattern. After accounting for overlaps, each of the elements is identified qu alitatively. By using previously calibrated

standard values the net counts for each element are converted to actual concentrations in

μ g/filter. Using air volume data gathered during sa mpling, the μ g/filter concentrations of the

elements are converted to μ g/M 3

.

QA/QC- The X-ray analytical instrument is calibrated using 35 single element standards. These calibration standards are checked using an NIST mul ti-element film standard. Filter blanks are analyzed for subsequent background correction durin g the spectral analysis of the run. Field blanks are taken at specified times depending on th e frequency of sampling. Field blank results are either subtracted or reported in accordance wit h data reporting and analysis requirements. Finally, collocated runs are utilized to check prec ision.MATES III Final Report

Appendix III-41 APPENDIX J Method Description for Sampling and Analysis of Ele ments by Energy Dispersive X-ray Fluorescence Spectrometry at the AQMD Laboratory

Sampling- Ambient air is drawn through a 47 mm Teflon filter loaded in a TSP or PM 2.5 sampler. Typically, 24 hour sampling at about 20 lpm provide s sufficient sample mass on the filter for a successful analysis. The sampler must collect a ho mogeneous sample across the surface of the filter. The Kevex XRF instrument examines a very s mall cross section of the filter near the

center.

Laboratory Analysis- A Kevex Energy Dispersive X-ray fluorescence spectr ometer is used to analyze 35 elements in the filter sample. There is no need for sample preparation other than bringing the filters to room conditions. Each filt er is loaded onto a sample wheel brought to a

vacuum and scanned under five different instrumenta l conditions. Each condition is optimized for certain groups of elements. After spectral acq uisition, an identification and de-convolution process extracts the net contributions of counts of each of the 35 elements.

Speciation and Quantification- Each element has a unique spectral pattern. After accounting for overlaps, each of the elements is identified qu alitatively. By using previously calibrated

standard values the net counts for each element are converted to actual concentrations in

μ g/filter. Using air volume data gathered during sa mpling, the μ g/filter concentrations of the

elements are converted to μ g/M 3

.

QA/QC- The X-ray analytical instrument is calibrated using 35 single element standards. These calibration standards are checked using an NIST mul ti-element film standard. Filter blanks are analyzed for subsequent background correction durin g the spectral analysis of the run. Field blanks are taken at specified times depending on th e frequency of sampling. Field blank results are either subtracted or reported in accordance wit h data reporting and analysis requirements. Finally, collocated runs are utilized to check prec ision.MATES III Final Report

Appendix III-42 APPENDIX K Method Description for Sampling and Analysis of Org anic and Elemental Carbon by Thermal/Optical Carbon Analyzer at the AQMD Laboratory

Sampling- Ambient air is drawn through a 47-mm quartz filter loaded in a PM 2.5 sampler or an 8 x 10 inch quartz fiber filter loaded in a SSI-Hi-Vo l sampler. Typically, 24-hour sampling provides sufficient sample mass on the filter for a successful analysis. The sampler must collect a homogeneous sample across the surface of the filt er. A one-centimeter diameter punch from any quadrant of the filter is used in the instrumen t.

Laboratory Analysis- A Desert Research Institute (Reno, Nevada) thermal/ optical carbon analyzer is used to determine the total carbon cont ent of aerosol deposited on quartz filters. The analyzer is able to distinguish and characterize or ganic and inorganic carbon by a thermal/optical

method with flame ionization detection. There is n o need for sample preparation other than bringing the filters to room conditions. A small c ircular filter area is punched out from the quartz filter and loaded on to the carrier quartz tube. T he filter is pushed into an oven whose temperature is raised in steps from ambient to appr oximately 850 degrees Celsius. An inert gas, such as nitrogen is continuously passed over the fi lter. At the same time the surface of the filter

is monitored with a laser beam to determine the exa ct point at which all the elemental carbon (soot) is burned off. The combusted carbon forms c arbon dioxide that is carried over to a methanizer. The methanizer (active nickel with the addition of hydrogen gas) converts the

carbon dioxide to methane. The methane flows to a flame ionization detector. The detector output is integrated and converted to μ g of carbon per filter using previously calibrated standards.

Speciation and Quantification- The light organic fraction is driven off the filter at the early stages of heating. The elemental carbon fraction i s then oxidized at a higher temperature with an oxygen enriched carrier gas. A laser beam constant ly scanning the filter surface indicates the exact point at which the organic and elemental carb on fractions are removed from the filter. The two fractions are summed to give the total carbon c oncentration of the sample. The analysis results in the elemental, organic, and total carbon content of the sample. Using air volume data gathered during sampling, the μ gC/filter concentrations are converted to μ gC/M 3 of air.

QA/QC- The optical-thermal carbon analyzer is calibrated u sing two types of standards. One set consists of carbon containing gases, methane and ca rbon dioxide in an inert gas mixture. These are passed through the entire system to calibrate t he instrument. In addition, filters impregnated with solution containing a known concentration of c arbon are run as external standards. Filter blanks are analyzed for subsequent background corre ction during the run. Field blanks are taken at specified times depending on the frequency of sa mpling. Field blank results are either subtracted or reported in accordance with the data reporting and analysis requirements. Finally, collocated runs are utilized in checking precision.MATES III Final ReportAppendix III-43APPENDIX L QA/QC Matrix SummaryProcessIntervalActivityCriteriaCorrective ActionBefore & After EachSampling EventQC - Note Activities in Log Book, CanisterTag, Chain-of-CustodyNotes For Each CanisterN/AQC - Check Chart Time±10 Minutes of Actual PSTAQIS ResetsField CanisterAnnually QC - Clean Manifold Pass Leak CheckAM Support RepairsSamplerQC - Calibrate Flow±5 % True FlowAM Operations Calibrates1 Day in 3 QA - Collocated Sample 10 % Of NetworkRun A + B Make-Ups if PossibleAnnually QA - ARB Through-the-Probe AuditWithin±25 % of True For all CompoundsIsolate & Repair, Validate DataQA - Flow AuditIndicated Flow Must Be Within±10 % of True FlowNotify Operations If Outside Limits, Delete DataBefore & After Each QC - Note Activities in Log Book N/AN/ASampling Event QC - Check Start & Stop Times & VolumeFor Each Sample.Note On Canisters Log Sheet AQIS Resets TimeField CarbonylQC - Clean Manifold Pass Leak CheckAQIS Cleans & TestsSamplerAnnually QC - Calibrate Flow Controller±5 % True FlowAM Operations CalibratesIf Equipment 1 Day in 6 QA - Collocated Sample 10% of NetworkRun A + B Make-Ups if PossibleAvailable Annually QA - Through-the-Probe Audit ByARBWithin±25 % of True For All CompoundsIsolate & Repair, Validate DataQA - Flow AuditIndicated Flow Must be Within±10 % of True FlowNotify Operations if Outside Limits, Delete DataQC - Chain-of-custody Log Sheet & Cartridge Numbers Agree Chemist Corrects Any ErrorsQC - Propane Peak±10 % Of PreviousChemist Adjusts SpanDaily QC – System Blank < 10 ppb/C Total NMOCChemist Repairs/ Leak ChecksQC – Replicate Sample Visual Evaluation of Chromatogram Chemist Repairs/Leak ChecksLaboratoryGCSemiannually QC – Replicate Standard Analysis±10 % on All CompoundsChemist RepairsQC - Bias Check 2 ppb/C Per CompoundChemist Repairs/Leak ChecksAnnually QC - LOD Check All Loads Must Be Less Than1 ppb/C Chemist Repairs/Rechecks1 Day In 6 QA – Collocated Samples±25 % On All CompoundsChemist RepairsQuarterly QA – Parallel SamplingAll Compounds Must Be Within±30 %Annually QA – NPAP Performance AuditWithin±30 % of True For All CompoundsChemist RepairsQC – Standard Response±10 % of PreviousChemist Repairs/Adjusts SpanDaily QC – Purge Cycle System Pressure Between 800& 1700 PSIG Chemist Leak ChecksLaboratoryCarbonylSemiannually QC – Multipoint Calibration±10 % Of PreviousChemist Develops New Calibration CurveQC - Bias Check <3 ppb Per CompoundChemist RepairsAnnually QC - LOD Check <1 ppb Per CompoundChemist Repairs/Leak ChecksQuarterly QA – Parallel SamplingAll Compounds Must Be Within±30 %Annually QA – NPAP Performance AuditWithin±30 % of True For All CompoundsChemist RepairsBefore & After Each SampleRunQC - Note the Maintenance Sheet, LogBook, & Sample EnvelopeNotes as RequiredN/ASemiannually QC – Change Motor & MultipointCalibrationCreate New Calibration Curve N/AQC - Clean InletField PM10SSIAnnually QC - Timer Check Timer Tested For Start With 20 Minutes of Setting & ElapsedTime to Within 20 MinutesRepair or Replace1-Day-in- 6 QA - Collocate Run At 10 % Of SitesN/AAnnually QA - Flow AuditActual Flow Must be Within±10 % of True FlowRequest Repair; Investigate & Confirm Data ValidityQC - Balance ChecksLaboratoryDaily QC - Inspect Filters No Light Leaks or TearsPM10SSIQC - Equilibrate Filters1 Day in 6 QA - Collocate FiltersAgreement Within±20 %, all CompoundsMATES III Final Report

Appendix III-44 Appendix M Method Description for Sampling and Analysis of VO Cs by GC/MS at the AQMD

Sampling - Ambient air is pumped into an evacuated Summa® po lished 6 liter canister by a Xontech 910A air sampler at the sample location t hrough a properly sited probe and manifold. The sample is integrated over 24 hours t o fill the canister to approximately 10 PSI. The canister is returned to the laboratory fo r subsequent analysis by Gas Chromatography with a Mass Spectrometer Detector (G C/MS).

Laboratory Analysis - The Laboratory uses a Hewlett-Packard 6890 Gas Ch romatograph with an HP 5973 Mass Selective Detector. The sampl e is concentrated with an Entech 7100 cryo-concentrator for input to the GC/MS. The sample canister is attached to the cryo-concentrator and a 400-milliliter aliquot (600 ml for MSS samples) is chilled in a trap to minus 150 degrees centigrade. For removal of the fixed gases the trap is heated to 20 degrees centigrade and transferred to a second t rap cooled to -45 C for mitigation of

the CO 2 and H 2 O collected. The concentrator loop is then heated and the contents cryofocused at the head of the GC column for subsequent separation of the VOCs. The mass selective detector records the mass spectrum of eac h peak (compound) and the analyst uses previously determined standards to compare sel ected ions for each compound to

determine the concentration.

Quantitation - A calibration curve is derived by injection of a gas standard containing the compounds of interest at ppb levels. Every sample run is preceded and ended with a calibration check. Every analysis day is begun wit h a system blank run. Selected quantitation ions for each compound are compared to the gas standards injected to determine concentration in parts per billion.

QA/QC- The Limit of Detection (LOD) is determined for the GC/MS by multiple injections of the lowest standard amount available (within 10 times the estimated LOD). Collocated samples are run in the field at one stat ion. All canisters from the canister cleaning system are filled with the purified nitrog en and tested for the presence of the compounds of interest. Above 0.2 ppb of any compou nd of interest or 4 ppb total of all compounds (ppbc) is cause for corrective action.