DESCRIPTION OF THE TEI MODEL 17C NH 3 ANALYZER, CALIBRATOR, AND ZERO AIR SUPPLY

Transcription

1 REDUCED NITROGEN (NH 3 ) MONITORING WITH THE TEI MODEL 17C ANALYZER DESCRIPTION OF THE TEI MODEL 17C NH 3 ANALYZER, CALIBRATOR, AND ZERO AIR SUPPLY C Operating Principle Instrument Specifications and Components Description (17C) C Analyzer Startup and Shutdown C Operating Principle Operating Principle (Model 111 Zero-Air Supply System) C Description of Controls Calibrator Functions Zero Air Supply Start-up and Operation REGIONAL RESPONSIBILITIES AND ASSIGNMENTS Site Calls Site Visits Operational Checks Unadjusted Calibration Adjusted Calibration Data Acquisition = Data Reporting for Regional Offices ( ) = Data Validation for Regional Offices ( ) Quality assurance procedures Preparation of the Data Assessment Report APPENDICES APPENDIX B.1 AQ-98 APPENDIX B.2 Logbook and Operational Test Form APPENDIX Replacing Capillaries APPENDIX M Troubleshooting the 17C Analyzer END OF SECTION 2.22: REDUCED NITROGEN (NH 3 ) MONITORING. 1

2 Section Revision No.0 07/31/01 Page 1 of DESCRIPTION OF THE THERMO-ENVIRONMENTAL (TEI) MODEL 17C AMMONIA ANALYZER AND CALIBRATOR The NH 3 monitoring system is described by separating it into two sections: the [17C NH 3 ] Analyzer and the [Model 111 and Model 146C] Zero-Air Supply and Calibrator, respectively. Together these components make-up the NH 3 monitoring station Principle of Operation (17C) The Model 17C Chemiluminescence Analyzer utilizes the reaction of nitric oxide (NO) with ozone (O 3 ) as its basic principle. Specifically: NO + O 3 NO 2 + O 2 + hν The sample is drawn into the Model 17C by an external pump. After it reaches the reaction chamber, it mixes with ozone which is generated by the internal ozonator. The chemical reaction above then takes place. This reaction produces infrared light with an intensity proportional to the concentration of NO. Specifically, light emission results when electronically excited N0 2 molecules decay to lower energy states. The light emission is detected by a photomultiplier tube, which in turn generates a proportional electronic signal. The electronic signal is processed by the microcomputer into a NO concentration reading. To measure the NO x (NO + NO 2 ) concentration, NO 2 must be transformed to NO prior to reaching the reaction chamber. This transformation takes place in a molybdenum converter heated to approximately 325 C. Upon reaching the reaction chamber, the converted molecules along with the original NO molecules react with ozone. The resulting signal represents the NO x reading. To measure the N t (NO + NO 2 + NH 3 ) concentration, both the NO 2 and NH 3 must be transformed to NO prior to reaching the reaction chamber. This transformation takes place in a stainless steel converter heated to approximately 825 C. Upon reaching the reaction chamber, the converted molecules along with the original NO molecules react with ozone. The resulting signal represents the N t reading. The NO 2 concentration is determined by subtracting the signal obtained in the NO mode from the signal obtained in the NO x mode. NO x - NO = NO 2 The NH, concentration is determined by subtracting the signal obtained in the N t mode from the signal obtained in the NO x mode. N t - NO x = NH 3 The Model 17C outputs NO, NO 2, and NH 3 concentrations to the front panel display and NO, NO 2, NH 3, and NO x concentrations to the analog outputs. Figure illustrates sample flow through the analyzer.

3 Section Revision No.0 07/31/01 Page 2 of Instrument Specifications and Components Description Model 17C Monitor Specifications Ranges 0-10, 20, 50, 100, 200, 500, 1000, 2000, 5000, 10000, ppb 0-100, 200, 500, 1000, 2000, 5000, 10000, 20000, µg/m 3 Extended Ranges 0-200, 500, 1000, 2000, 5000, 10000, 20000, 50000, ppb 0-500, 1000, 2000, 5000, 10000, 20000, 50000, , µg/m 3 Zero noise Lower detectable limit Zero drift (24 hour) Span drift (24 hour) Response time (O - 90%) Linearity Sample flow rate Operating temperature Power requirements Physical dimensions Weight 0.5 ppb RMS (120 second averaging time) 1 ppb 1 ppb 1 % full scale 120 Seconds (10 second averaging time) ± 1 % full scale 600 cc/min C (may be safely operated over the range of 5-40 C) /60 Hz /60 Hz /60 Hz 500 Watts (W) X 8.62 (H) X 23" (D) Analyzer (W) X 6.87 (H) X (D) Converter 60 lbs. (Analyzer Module - including external pump) 19 lbs. (Converter Module) Outputs NO, NO 2, NH 3, and NO x, selectable voltage, 4-20 ma, RS-232, RS-485

4 Section Revision No.0 07/31/01 Page 3 of 15 Model 17C Sample Flow Figure Theory of Operation (17C) In order to understand the operation of the Model 17C, a general knowledge of the electronics, software, and subassemblies is necessary ELECTRONICS The electronics can be broken down into the following subassemblies: DC Power Supply Photomultiplier Tube Power Supply Ozonator Power Supply Temperature Control Board Input Board Microprocessor System A brief description of each follows. Note that all the electrical schematics are given in Appendix C, "Schematics" of the TEI 17C Owner s Manual. a. DC Power Supply The DC Power Supply outputs the regulated and unregulated DC voltages necessary to operate the digital electronics, Input Board, and the Temperature Control Board. It outputs + 24 volts unregulated and + 15 volts and + 5 volts regulated. The DC Power Supply Board also contains the circuitry for driving the solenoid valves and a circuit for powering and controlling the photomultiplier cooler supply.

5 Section Revision No.0 07/31/01 Page 4 of 15 b. Photomultiplier Tube Power Supply The Photomultiplier Tube (PMT) Power Supply provides the PMT with the negative high voltage required for operation. The power supply output may be adjusted from about -500 to volts DC. c. Ozonator Power Supply The Ozonator Power Supply provides the ozone transformer with approximately 55 Hz, 15 volt pulses which the transformer steps up to about 15 kilovolts. The timer, U5, generates a square wave which feeds U3. This IC generates pulses which feed the network composed of U2, C2, C3, R4 and R5. This network acts to turn Q1 and Q2 on and off in a 4-step cycle. This cycle results in the discharge of C1 and C5 through the transformer generating high voltage pulses which power the silent-discharge ozonator. d. Temperature Control Board The Temperature Control Board regulates and sets the temperature of the converter and the reaction chamber. The converter temperature is measured with a type K thermocouple. The thermocouple voltage is conditioned by U4, which supplies a voltage output of 10 mv per C. The conditioned signal is compared to a reference signal set by a potentiometer, and the comparator output is used to turn the heating element on and off. Both the converter set temperature and the conditioned thermocouple signal are picked up by the microprocessor and are used to display the actual converter temperature, as well as the converter set point. The reaction chamber temperature is measured with a thermistor, whose resistance is equal to that of the reference resistor at approximately 50 C. The voltage across the thermistor is used by the microprocessor system for use in calculating and displaying the reaction chamber temperature. e. Input Board The Input Board accepts the current signal from the PMT and converts it to a voltage through a 100 megohm feedback resistor (RIO). This voltage is scaled by about a factor of 1, 10, or 100, depending on the fullscale range of the NO channel. The scaled voltage signal is converted to a pulse train by the V/F converter and sent to the microprocessor. A switch on the Input Board turns a test signal on and off which is injected at the first stage of the Input Board in parallel with the PMT input. This allows the Input Board and the connection to the processor system to be tested without using the PMT. f. The Microprocessor System The microprocessor system consists of printed circuit boards which plug into the Motherboard, connecting them to each other and to the rest of the instrument. These boards are as follows: Display Module Processor Board Analog to Digital Board Digital to Analog Board

6 C-Link Board Section Revision No.0 07/31/01 Page 5 of 15 Display Module. The vacuum fluorescent display module shows NO, NO 2, and NH 3 concentrations, instrument parameters, and help messages. The single board display module consists of 80 characters (4 line by 20 column), refresh memory, character generator, DC/DC converter and all necessary control logic. The display module is powered by ±5 volts DC. Processor Board. The Processor Board contains a Motorola M68HC11F1 microprocessor (U4), RAM (U5), and EPROM (U2). In addition, this high performance, non-multiplexed 68-pin microprocessor contains 512 bytes of EEPROM and 1K of RAM. It is operated at a frequency of 2 MHz, which is generated by crystal X1. During each instruction cycle, the processor fetches an instruction from memory and executes it, reading or writing data to or from the data bus, or performing a calculation on some internal register or registers. The reset signal is generated by U8. This signal resets the M68HC11F1 every tenth of a second, and is used by the microprocessor to keep track of time. Each time the microprocessor is reset, it reads the counters, increments the clock, checks the status of the pushbuttons, and updates the D/A converters and display. The MC64B40 counter chip (U1) acts as the interface between the Input Board and the microprocessor. A pulse train from the Input Signal Board is directly fed into one of three counters on the MC64B40 counter chip. Digital/Analog Board. The Digital to Analog Board contains four D/A converters, one for each analog output. Each is addressed by the processor via signals from PAO-PA7 and PGO and PGI. The D/A converters are zeroed using potentiometers R1, R3, R5, and R7 and span is set using potentiometers R2, R4, R6, and R8. The fullscale output of the four D/A converters is set by jumpers on switches SW1-SW4 on the D/A board. Fullscale voltages of 10, 5, 1, and 0. I volts are available. Analog to Digital Board. The Analog to Digital Board acts as an interface between all the signals monitored by the processor system and the microprocessor itself. Up to 12 analog inputs are available. The cooler temperature, reaction chamber temperature, internal temperature, pressure, power supply voltages, PMT high voltage, and flow rates are examples of analog signals converted to digital signals used by the microprocessor. C-Link Board. The C-Link Board contains the RS-232 circuitry, clock, and memory for the datalogger. Incoming RS-232 signals are converted to TTL levels by U3, an RS-232 driver/receiver. The TTL signals are then interpreted by U5, a 68HC11 microprocessor, which is dedicated to remote communications. Data records from the internal datalogger are stored in U2, a 128K RAM, and the link program is stored in U6, a 64K EPROM. U10 is the internal clock. A battery supplies +5 volts to the clock and the data logger memory when instrument power off SOFTWARE The software tasks of the processor can be broken down into four areas: a. Instrument Control Sixteen control lines are located on the Analog to Digital Board. Line 0 is used to turn the ozonator on or off. Lines 1, 2, 3, 4, and 5 go to the Power Supply Board and control the mode

7 Section Revision No.0 07/31/01 Page 6 of 15 solenoid valves, and any additional solenoids used for special applications. Line 6 is used to turn the PMT voltage on or off. Lines 13 and 15 go to the Input Board and control the gain of the preamplifier. The remaining lines are currently not in use. b. Monitoring Signals The monitoring of signals is tied to the tenth of a second cycle time for the processor system, and to the one and ten second intervals which are derived from this cycle time. Every tenth of a second, the processor is reset and the counters and pushbuttons are read. Once every second, the accumulated counts are sampled. The 1-second accumulated counts representing the NO/NO x /N t concentrations are further accumulated for a total of 7 seconds before they are processed, while the other 1-second accumulated counts representing other signals are processed directly. Every ten seconds, the NO/NO x /N t solenoids switch and the processor waits 3 seconds for the reaction chamber to flush and stabilize. After those 3 seconds, it samples the signal intensity for 7 seconds before again switching the solenoids. c. Instrument Calculations The calculations of the NO, N0 2, NO x, NH 3 and N t concentrations are lengthy and utilize the processor to provide the most accurate readings. The calculations begin by subtracting the appropriate electronic offsets from the 7 second count accumulations. There are three such offsets, one for each of the three settings on the input board. This software based correction provides excellent cancellation of any electronically induced offsets and eliminates the need for potentiometer adjustments on the input board. Following this correction, the raw accumulated counts are scaled according to the gain setting of the input board. Next, the uncorrected NO, NO X, and N t values are determined according to a unique averaging algorithm which minimizes errors resulting from rapidly changing gas concentrations. This algorithm results in NO, NO x, and N t values which are stored in RAM in a circular buffer that holds all the 10 second data from the previous 5 minutes. This data is averaged over the selected time interval, which can be any multiple of ten between 10 and 300. The background values for in NO, NO x, and N t, which are corrected by the stored calibration factors and by temperature factor, are subtracted from their respective averages. The NO reading is corrected by the stored span factor and by the temperature factor. The NO x reading is partially corrected by the span factor, temperature factor, and balance factor. The N t reading is partially corrected by the span factor, temperature factor, and balance factor. The corrected NO value is subtracted from the partially corrected NO x value to yield an uncorrected NO 2 value. The NO 2 value is then adjusted for converter efficiency to give a corrected NO 2 reading. The corrected NO 2 reading is added to the corrected NO reading to yield a fully corrected NO x value. The corrected NO x value is subtracted from the partially corrected N t value to yield an uncorrected NH 3 value. The NH 3 value is then adjusted for converter efficiency to give a corrected NH 3 reading. Finally, the corrected NH 3 reading is added to the corrected NO,, reading to yield a fully corrected N t value. d. Output Communication The front panel display and rear panel analog outputs are the chief means of communicating the results of the above calculations. The display output is coded with 1 representing the NO output,

8 Section Revision No.0 07/31/01 Page 7 of 15 2 the N0 2 output, 3 the NO x output, 4 the NH 3 output, and 5 the N t output. The decimal point on the display automatically shifts in response to changes in gas concentration. The three analog outputs do vary according to the range. They are calculated by dividing the data values by the fullscale range for each of the three parameters and then multiplying each result by Negative concentrations can be represented as long as they are within -2.3 % of fullscale. This gives numbers between -23 and 1000, which are used to drive the three, 10-bit digital to analog converters SUBASSEMBLIES a. Photomultiplier Cooler The thermoelectric cooler houses the PMT. The PMT is of the multi-alkali type in order to have the infrared sensitivity required to detect NO 2 luminescence. The PMT is cooled to about -16 C to reduce dark current and increase instrument sensitivity. The cooler is also controlled at this temperature in order to have increased zero and span stability over a wide ambient temperature range. b. Reaction Chamber The reaction chamber subassembly is an integral part of the cooler assembly. It is a two-piece 24 carat gold plated assembly which design allows for ease of cleaning and maintenance. In this reaction chamber, the sample reacts with ozone, producing excited N0 2 which in turn decays, giving off a photon of energy. The reaction chamber is heated and controlled to approximately 50 C in order to ensure the greatest instrument stability. Also housed in the reaction chamber assembly are the sample and ozone flow capillaries and a thermistor sensor. c. N0 2 -to-no Converter The N0 2 -to NO converter employs molybdenum heated to approximately 325 C in order to convert and detect N0 2. The converter consists of an insulated housing, heater, replaceable cartridge, and a type K thermocouple sensor Front Panel Controls The Model 17C uses menu driven software with Entry Pushbuttons to set the operational parameters and an acceptable range of operation for the analyzer. The Front Panel of the analyzer, with a description of Entry Pushbutton functions, is shown in Figure (a), and a flowchart of the menu driven software and subroutines is presented in Figure (b).

9 Section Revision No.0 07/31/01 Page 8 of 15 Figure (a): Front of Model 17C Pushbuttons - There are eight pushbuttons that are used to engage different modes of operation through menus for calibrating and Gas Phase Titrations. The 17C is based on menu-driven software as illustrated by the flowchart in Figure (b). a. ENTER pushbutton used to choose a menu item, activate an entry, or toggle on/off functions. Use the ENTER pushbutton to choose or accept a menu item or a value. b. MENU pushbutton used to display the main menu and the submenus containing instrument parameters and the features of each main menu item. Also, use this pushbutton to return to a previously displayed menu, e.g. if a mistake is made. c. pushbuttons move the cursor up, down, left, or right to a specific menu item or digit in a setting and increase or decrease (INC/DEC) the value of a setting in a menu. d. RUN used to display the present or active settings of the 17C in the Run Screen. The Run screen normally displays the NO, NO 2, and NH 3 concentrations.

10 Section Revision No.0 07/31/01 Page 9 of 15 Figure (b): Flowchart of Menu driven software Analyzer Startup and Shutdown A. Startup 1. With the power switch ON, all electronics are turned on, the converter turns on, the cooler, the reaction chamber heater, and the program initialize itself. Turn on the sample pump which should be pumped to the exhaust port on the analyzer. Exhaust pump through the charcoal filter and vent to the outside. During the first few minutes of operation the word "HELLO" is followed "NO-NO 2 " during which time the analog output will be 0 volts. The instrument will automatically go into the "Run-Sample" mode. 2. The Model 17C has been designed so that pushbutton functions do not disturb analog outputs. When in the Run mode, the NO, NOx, and NH 3 output is available. Note that the Model 17C requires both the cooler and converter to reach and stabilize at their respective operating temperatures before meaningful data is obtained. It takes approximately one and a half hours for the Model 17C to stabilize if the power is off for several hours. The ozonator should be left ON over night before any initial calibration or recalibration and after a long down period of more than several hours. Note: If the analyzer is going to be down for more than several hours, follow the steps below. Complete only step 1 below for shorter periods of inactive use.

11 Section Revision No.0 07/31/01 Page 10 of 15 B. Shutdown 1. Push the "POWER" switch OFF on the front panel of the control section. All internal components of the Model 17C should now be shutdown. Caution!!! If repair work is done on the control section, remove the line cord from the back to totally eliminate any shcok danger DESCRIPTION AND OPERATION OF TEI MODEL 146C AND ZERO AIR SUPPLY Operating Principle (Model 146C Calibrator) The Model 146C Calibrator supplies the required levels of nitric oxide and nitrogen dioxide to perform zero, precision, span checks and multipoint calibrations. The Model 146C will be operated remotely from the datalogger to perform zero and no span checks. The Model 146C is basically a combination of two devices in one convenient package: 1. an accurate mass flow controlled gas dilution system, and 2. a gas-phase titration system. NO gas from a NIST traceable Protocol II certified cylinder (connected to Port A) is blended with "zero-air" to provide a desired concentration. From the known calibration of the two mass flow controllers, the exact concentration can be calculated. Typically a dilution ratio of about 100:1 to 1000:1 is used. To generate the desired levels of ozone, the cylinder gas flow is turned off, the zero-air mass flow controller is set to the desired flow, and the ozone generator is activated. The ozone level at constant flow is changed by varying the voltage to the ozone generator lamp. The photolytic ozone generator used on the Model 146C passes all U. S. EPA qualification tests for an ozone generating transfer standard. The nitrogen dioxide (NO 2 ) concentration levels are generated by mixing known amounts of NO from the cylinder with ozone. The amount of NO 2 formed is equal to the measured decrease in the NO level. The decrease in NO level is determined using the NO channel of the Model 17C analyzer. This technique of determining pollutant concentrations is known as gas-phase titration. The volume of the reaction chamber (i.e., 150 cc) has been chosen to meet the dynamic parameter requirements of the U.S. EPA. The Model 146C contains an LCD readouts to display the actual flows measured by the mass flow controllers, one for zero air flow and one for cylinder gas flow. The sample/span solenoids for the Model 17C analyzer should be connected to the analyzer inlet port. These solenoids can be controlled by signals from the Model 146C. Note that the plumbing should be set-up so that both sample and span gases pass through the particulate filters as required by U. S. EPA requirements. The flow of the Model 146C should be set to satisfy the flow demands of the NO analyzer connected to the calibrator. The manufacturer claims that ozone generator can be calibrated using an ozone primary standard if it is to be used for ozone monitor calibration, and that it will pass EPA's requirements as an ozone transfer standard.

12 Section Revision No.0 07/31/01 Page 11 of Operating Principle (Model 111 Zero-Air Supply System) The purpose of the Model 111 is to supply pollutant-free air ("zero air") for proper zeroing and to provide clean diluent air for spanning ambient air analyzers. The components to be removed are SO 2, NO, NO 2, O 3, CO and hydrocarbons. There is no consensus as to what extent "zero air" should have water vapor removed. Since many analyzers have longer response times if super-dry (dew point less than -30 O C) is used for zero and span, and since water vapor is not a pollutant, the Model 111 does not have a drying system. However, the dew point is reduced as a result of compression of the ambient air. Room air enters the compressor, where it is raised to a pressure of approximately psi (4560 mm). At 25 O C, the saturation water vapor pressure is approximately 24 mm. Thus most of the water condenses out and falls to the bottom of the tank. Out of the 4560 mm of pressure in the tank, only 24 mm is due to water vapor. When this air is vented to atmospheric pressure (760 mm), the water vapor is reduced to approximately 4 mm. This corresponds to a dew point of slightly less than 0 O C. In order to keep any condensation from occurring in the tubing between the compressor and the Model 111, the output of the compressor contains a coalescing filter and a pressure regulator where the pressure is reduced to 70 psi. Inside the main case of the Model 111, the compressed air is further reduced to the final desired pressure (10-30 psi). The air then goes into the reactor where it is heated to 350 O C over a catalytic surface that converts CO to CO 2 and hydrocarbons including methane to water and CO 2. The air then passes into a column of Purafil (potassium permanganate on alumina) that oxidizes NO to NO 2. Finally, the air passes through a column of iodated or activated charcoal that removes NO 2, SO 2, O 3, and hydrocarbons. This results in a pollutant-free air stream Description of Controls (Model 146C Calibrator) 1. Power - Activates the AC power for the Model 146C Calibrator. When turned on there will be an audible sound from the internal fan, the power switch light will go on, and the LCD displays of the flowmeter will be on. 2. LCD flow displays - Anytime you run an event in REMOTE or LOCAL mode, the LCD will display the zero and gas flow, the output ppm and the active mode the 146C is in (REMOTE or LOCAL). The NO gas mass flow controller has a range of 0 to 100 SCCM, and the zero air mass flow controller has a range of 0 to 10 LPM. 3. Pushbuttons - There are eight pushbuttons that are used to engage different modes of operation for calibrating and GPT s. The 146C is based on menu-driven software as illustrated by the flowchart in Figure a) ENTER pushbutton used to choose a menu item, activate an entry, or toggle on/off functions. Use this pushbutton to change to the Local or Remote `mode. b) MENU pushbutton used to display the main menu and the submenus containing instrument parameters and features of each main menu item. To return to the previous displayed menu press this pushbutton. c) pushbuttons used to move the cursor up, down, left, or right to a specific menu item or digit in a setting and to increase or decrease (INC/DEC) the value of a setting in a menu. Use the ENTER pushbutton to choose or accept a menu item or a value.

13 Section Revision No.0 07/31/01 Page 12 of 15 d) RUN used to display the present or active settings of the 146C in the Run Screen (it tells where you are at this moment). Also used to cycle through the calibration points and the GPT options. Figure Flowchart of Menu-Driven Software for the 146C 4. Description of selected submenus a) MANUAL SETTINGS are used to manually control the zero air and gas flows for the GPT mode. To do a gas phase titration, you must manually duplicate the zero and gas flows in the span. Use this menu for that purpose. Use the pushbuttons in section 3 above to input the pertinent information. b) AUTOMATIC SETTINGS are used to set flow rates in the Gas Dilution modes to allow automatic calculation of the output PPM of the dilution of GAS A, B, or C in calibrations. The operator must input cylinder or tank PPM in the Gas Dilution Screen. Up to five span levels can be set. Use the pushbuttons in section 3 above to input the pertinent information. c) SET GPT/GAS A - Activation of this menu item deactivates the other gas modes and causes the solenoids in the Model 146C to switch the ozone generator into the flow of GAS A (NO) going into the output manifold. The ozone generator activates. In addition, the solenoid terminal on the back of the Model 146C labeled ozone becomes active. To perform a gas phase titration with the 17C, both the ozone and Gas A menu items must be active. Other gases, GAS B and C, will not react with ozone in the 146C reaction chamber. Note that when the reaction chamber is in the flow circuit the response at the output manifold is slow (approximately 5 minutes to >95% of final value).

14 Section Revision No.0 07/31/01 Page 13 of 15 d) GAS A DILUTION (ZERO AIR and GAS A Flows)- Activation of this menu item causes the solenoids in the Model 146C to switch to Gas A into the mass flow controller (MFC) and set the other flow solenoids for the dilution mode. In addition, the solenoid terminal on the back of the Model 146C labeled A becomes active. Typical gas and zero flows should always be % of the flow range of the MFC. In addition, supply at least 2 LPM of total flow to the 146C and at the same time maintain the gas and zero air flow limits of %. Different calibration flow gas levels are pre-programmed into the 146C by the ECB. c) O3 LEVEL - The ozone level can be increased or decreased by using the pushbuttons while in the GPT run screen. The ozone level is determined by comparison to an ozone primary standard. The ozone level is a function of both the potentiometer setting and zero and gas flows; therefore, changing either will change the ozone level Calibrator Functions A. Start-Up 1. Activate the power switch. If only the dilution mode of operation is desired, no warmup time is necessary. If the ozone generator is being used, about 15 minutes warm-up time is required. Note: The ozone forming lamp will not ignite until the ozone generator is at operating temperature. 2. Set the flow levels and ozone levels using the pushbutton potentiometers as in ECB section and See Section for calibration of the 146C Mass Flow Controllers and section F for computing NO gas levels from these known flows. 3. Wait for a stable reading from the analyzer being spanned or calibrated. Except for the gas-phase titration mode, the Model 146C has a response time to better than 95% of final value of less than 30 seconds which is generally the analyzer time constant that is the rate determining time constant. 4. Repeat 3 and 4 above for other concentration levels if desired. B. Standby There should always be a source of zero-air connected to the Model 146C. Stanby is the default mode that the 146C will revert to if left undisturbed for one-hour in Local Mode. To manually put the Model 146C into the standby mode conduct the following step: 1. From the Flow Modes menu choose Standby 2. Press ENTER to accept C. Shutdown To shutdown the Model 146C, turn the power switch off. D. Loss Of Power If the power switch is left in the ON position and a power failure occurs, the Model 146C will turn on, upon resumption of power. E. Remote Operation This mode allows the 146C to be controlled by data logger events. Remote operation of the Model 146C is similar to the manual operation. If the remote device has the capability and is connected all mode commands that can be performed manually can be

15 Section Revision No.0 07/31/01 Page 14 of 15 performed remotely. For NH 3 monitoring, when you are in running in Remote Mode, it means you are either running a zero or a span. All other levels for NH 3 monitoring are activated through the Local Mode. You cannot adjust any settings while in the Remote mode. F. Local Mode This mode takes precedence over the Remote. Local mode allows the operator to control the data logger via the front panel of the 146C. You should not go to Local Mode unless you start a Remote event. Note: Going to Local Mode WITHOUT a Remote event running could damage the instrument. The 146C will interrupt the Local Mode by switching back to Remote after one-hour. To prevent this, press Run while in Local Mode to cycle through the options until you are back to the original option - the one you are running. (For example, if you are running a GPT and go to eat a one-hour lunch without cycling through the options before you leave or right when you come back, you will find the 146C no longer running the GPT, but instead running the last Remote event. This means running the span and GPT all over again). G. Computation Of Concentrations The computation of the different output levels for the different modes of operation are as follows. Note that it is assumed that all devices are properly calibrated and that all flows are generate a span gas with a concentration of 45 ppb NO, use the following equation corrected to 25 O C and 1 atm in accordance with Section For example, to: Model 146C Output = F GAS Conc. Cyl. F GAS + F ZERO where F GAS = NO gas flow F ZERO = zero air flow Conc Cyl = concentration of NO or NH 3 cylinder gas (Note: NO y cylinder concentration may be slightly higher as it sometimes contains an NO 2 impurity.) The TEI Model 17C NH3 analyzer blends zero air and NO gas at the dilution ratio of 100:1. The Model 17C NH3 analyzer has a minimum flow requirement of 2000 SCCM delivery at atmospheric pressure. Based on a constant zero air flow of 5000 sccm/min, and the NO gas flow (Fgas), the 146C output becomes approximately 50 sccm based on the 100:1 ratio. Actual flows of NO, NH 3 and zero air are determined from the Protocol NO gas concentration and from multiplying the LCD readings of the NO and zero air channels by the slope and intercepts of the corresponding calibration curves. This calculation is done in a microprocessor housed in the 146C Calibrator. A flow calibration procedure is provided in section (ECB) Zero Air Supply Start-up and Operation 1. Close manual valve on output of compressor. Plug in compressor. The pressure in tank should gradually increase to psi. At that point the pump should shut off. 2. Open manual valve. Adjust pressure regulator downstream of coalescing filter to 70 psi. Adjust pressure regulator on Model 111 case for desired pressure (typically psi).

16 Section Revision No.0 07/31/01 Page 15 of Turn dial on temperature regulator to 350 C. Turn on the Model 111. The internal cooling fan should start blowing. The light on the temperature controller should go on. 4. After ½ to 1 hour the LED on the temperature controller should be cycling on and off indicating that the reactor is up to temperature. The Model 111 is now ready for use. 5. The compressor motor should cycle on and off with the tank pressure being controlled between 80 and 100 psi.

17 Section Page 1 of SITE OPERATOR S RESPONSIBILITIES AND ASSIGNMENTS Sites are equipped with ETC-6002 data loggers, and ESC-8816 "back-up" data logger. Both are important tools in reviewing monitor/site operations. To ensure the calibrator and monitor zero/spans are within required ranges, an automatic zero/span check is performed. The NO x and NH 3 zero/spans are checked automatically. The NO x and NH 3 precision points must be checked manually at least every two weeks (14 days). Additionally, the NO x converter efficiency must also be calculated every two weeks (see section ) SITE CALLS To minimize travel, some site operational checks must be made by telephone. Site calls are recommended on every day of the workweek. Calls to a site can be made at any time; except during the first 5 minutes of an hour. The data logger will answer and provide an automatic hourly report to your terminal during this period. If the site does not answer, a site visit should be made to determine the problem Site Calling Connect the computer modem to the telephone jack. Use communications software (e.g. HyperTerminal or ProComm) to log on to the site computer and communicate with the site data loggers. When the data logger asks, enter the PASSWORD As a minimum request, "D" (today's data), "Y" (yesterday's), if calling on a Monday, "2" (day before yesterday's data), and after obtaining those, request "F" (power failures). Note any recent power failures Flagged Data Review Flags (symbols) are assigned to data to indicate its validity. If no flag follows a value, the data is assumed accurate and valid. These data are in all appropriate averages. Flags that do not invalidate data are as follows: Flag Meaning < missing data, but above completeness criteria ~ high alarm - low alarm \ rate-of-change alarm Flags used to indicate invalid data are as follows: Flag Meaning Priority F Power failure Highest D Parameter marked down B Bad status input C Calibrate P Purge Lowest Data accumulated under the above conditions will be flagged and considered invalid. Data from zero and span checks are entered into logs under zero/span (OSC) results Compare any flagged data with what is expected to occur (ie. low data at times of low source emissions, missing data during auto zero/span times). If any of the flagged data appears unusual make a note to check the Backup data logger during the next site visit. If

18 Section Page 2 of 27 several values are invalid, a site visit may be needed. If a channel is incorrectly marked D (down) (by a previous incorrect action), the data may be valid and you will need to notify headquarters of any valid data to be reported. Do this by sending in an AQ-42 for the incorrectly flagged valid data. To remove the "D" flag, press "ESC" if necessary, type U, and type in the channel(s) to be "Upped", Enter, and Enter again Site Temperatures Review Review site temperatures by comparing the TMP channel data to the 20 C to 30 C allowable range. If any TMP data are outside of this range, make a note to adjust the site thermostats on the next site visit; and also notify the QA Coordinator for guidance concerning data validity Review Auto Zero Span Check (AOSC) Results The AOSC appearing at the end of each day's data was conducted between 00:00 and 5:00 AM of that day Compare the monitor zero results to the theoretical calibrator zero for each day. If each day's paired zero results do not agree within ±5 ppb, a site visit is required to conduct an adjusted calibration ( ) Compare the theoretical calibrator NO x and NH 3 auto spans to the analyzer NO x and NH 3 span output for each day. If each day's paired span results do not agree within ± 10%, a site visit is required the same day (unless a reasonable excuse can be provided) to conduct an unadjusted calibration. If both zeros and spans checked agree with the ranges given above, a manual unadjusted calibration according to , may or may not be required depending upon the frequency of site visits Power Failure Report Review the power failure report received in above. By using an AQ-42 note any power failures of greater than 5 minutes and invalidate the 20-minute period of data following the power failure Current Data Review If necessary press ESC, and enter "M", and type the number for one of the NO x / NH 3 and the TMP channels to review the current data. Press Enter when asked. If any data is flagged or appears unusual, determine if a site visit is needed. You may run a "NO" OSC by pressing ESC and entering "C", entering the 6 character access code, and answering the questions to start either a span or zero as appropriate (see ). Do not forget to stop the OSC when finished Hanging Up Before "hanging-up" review the current data to be sure no flags (D, S, Z, etc.) are indicated in the data printouts. If there are, be sure to return the monitoring system to its normal sampling mode by "upping" the channels or stopping the OSC. The data logger will clear the P flag (purge). Before hanging up, log out of the PDL by typing!. "Hang-up" the modem to end the daily site review session. Make remarks on the "Site Call" printout and file the printout to document the call.

19 SITE VISITS Section Page 3 of 27 Unadjusted 4-point calibrations (see ) at concentrations of 90%, 50%, 16% (see for more on the 16% point), and 0% of full scale including the gas phase titration, are required every two weeks (14 days), and must be conducted before any instrument adjustments. The same points are used for an adjusted calibration except that the 16% point cannot be reported as a precision point when adjustments are made. No checks that affect data are to be made during periods of high ambient levels. Quality control checks at the beginning and end of a period of data collection are indicators of what data to validate or invalidate data over the period of data collection. In general, if a block of data turns to a questionable status, the data must be invalidated to the last acceptable check to assure good data quality. Throughout the NH 3 monitoring season, unadjusted and/or adjusted checks / calibrations must be performed following any one of activities listed below: = An interruption of more than two days in analyzer operation = Physical relocation of the analyzer (requires an adjusted calibration after relocation) = System Failures or repairs (pumps, ozonator lamps, capillaries, converters, and PMT s) = Excessive span drift (must check > ±10%) = Excessive zero drift (NH 3 > ±5 ppb; NOx > ±2 ppb). = Installation of a monitor, PDL, BUDL, or calibrator = Any repairs which might affect calibration. These repairs do not include multipoint calibrations, solenoid changes, and fan filter changes. An initial adjusted calibration is performed at site start-up without first performing an unadjusted calibration. All subsequent adjusted calibrations are only performed following an unadjusted calibration. The following tables have been inserted to help guide the operator as to conducting the appropriate checks when at the site for the above stated reasons: System Failure Type Action to take Pump ozonator Converter Contact ECB to replace bad pump and install new pump. Conduct an UCAL after new pump is installed. Call ECB for new ozonator. Conduct an ACAL after ECB replaces. Phone ECB to replace converter. Conduct ACAL after ECB replaces. May require a new monitor installation. Plugged Capillaries Replace capillaries according to the directions in appendix Operational Interruption that lasts more than two days ACAL Codes: U=Unadjusted; A=Adjusted; GPT=Gas Phase Titration; PC=Precision Check; Z=Zero; S=Span; CAL=Calibration An unadjusted or adjusted calibration means running the following four points and the GPT for each of the NO x and NH 3 channels (Note: the NH 3 converter does not require a GPT): (i) Zero (0) / (ii) Span point (90% of full scale) / (iii) Mid point (50% of full scale) / (iv) Precision (16% of full scale).

20 Routine Checks Action to take Span Drift > ±10% UCAL followed by ACAL if UCAL shows NH 3 span to be off by more than ±10%. Section Page 4 of 27 *To find the percent difference (drift) at any point, simply divide the difference between the measured (M) and theoretical (T) values by the theoretical value. Multiply that ratio by 100 to get the percent difference. The drift is positive when the measured value is greater than the theoretical value and negative when the measured value is less than the theoretical value: [(CM - C T) C T] x 100 = % drift. *Calibrator Replacement *ECB replaces calibrators; operators conduct the checks below UCAL UCAL UCAL Old Calibrator PASSES FAILS PASSES New Calibrator PASSES Action to take (Transfer Successful) UCAL with New Calibrator. NH3 span %diff s. of the old and new calibrators are within ±8 points of each other. Compare NH 3 span %Diff of both old and new. If span %Differences are not within ±8 points of each other, contact ECB for troubleshooting purposes. Otherwise install new **FAILS **NH 3 span % differences of the old and new calibrators are not within ±8 points of each other. Check New / Old shop. Contact ECB for calibrator and adjust if UCAL does notanother New Calibrator. meet the criteria in *Checks are only valid for a calibrator already in certification. Do not let a calibrator fall out of certification! Note: Do not perform checks or calibrations between 6:00 AM and 9:00AM "Local Standard Time". This is an important data collection period Computer Print-out Data Start a data printout sequence using a keyboard as follows: a. Turn on the screen and printer. b. Double click on Shortcut to Spltscrn icon located on the Windows 95 desktop. The PDL and BUDL Hyperterminal split screen windows appear. c. ALT-TAB to the PDL (Primary Data Logger) window. Note: Press ESC at any time to return to the > prompt on the PDL. d. Press Alt "S" and type "E" to turn on printer (The printer will only operate when the printer buffer is full). Another option is to capture text to file: Press Alt "T", scroll to capture text, name file in the following format: two character site code /parameter/date (yymmdd). For example a NH 3 calibration at Clinton Crops on should be saved as: "CCNH ". Press start. e. On the primary data logger type "!", and enter the 6-character password. At this point, you may select a number of reports that will provide information about the site operation As a minimum request, "D" (today's data), "Y" (yesterday's), if calling on a Monday, "2" (day before yesterday's data), and after obtaining those, request "F" (power failures). You

21 Section Page 5 of 27 may request other reports if desired. The "P" report will identify the channel number for each pollutant. Review the reports for flagged data Compare any flagged data with what is expected to occur (ie. low data at times of low source emissions, missing data during auto zero/span times). If any of the flagged data appears unusual, check the backup data logger. Determine and record the reasons for any truly invalid data. If a channel is incorrectly marked D (down) (by a previous incorrect action), the data may be valid and you will need to notify headquarters of any valid data to be reported. Do this by sending in an AQ-42 for the incorrectly flagged valid data. To remove the "D" flag, type U, and type in the channel(s) to be "upped", Enter, and Enter again Monitor Power On Check Verify the instrument has power by observing the display and listening for the pump. Record in logbook. If monitor does not have any power, determine the cause and time of power failure. Review the "F" printout - - power failure report. Invalidate data recorded for the 20 minute period following a power failure of greater than five minutes. Correct the cause and conduct a NO x /NH 3 zero and span. Record all events in the logbook. Notify supervisor Review the BUDL "graphs" as follows: a) Turn on the screen and printer. b) Double click the Graph Icon on the Digi-trends Screen. Choose one-minute data to graph. d) Select site and select parameter and enter. e) Enter date and hour of data to graph (to review) - mm, dd, yy, and then hh. Press enter and if correct respond with "y". f) Choose the number of hours to display and press enter. g) To scroll, press the > or < buttons allow you to scroll forward and backward in time. i) If you observe any unusual graphs, zoom in or out as needed (press F-1 for help as needed). It is suggested that the operator use the "Print Screen" key on the graphing toolbar to print copies of any unusual graphs which should be stapled in the logbook. j) To exit the chart viewing, press ESC as necessary to get back to the Main ESC Menu. Note: Visually inspect the "graphs" for any abnormalities such as a straight trace for several hours other than the minimum detectable limit, excessive noise as indicated by a wide solid trace, or a cyclic pattern of the trace (other than diurnal) with a definite time period indicating a sensitivity to change in temperature or pollutant other than NO x and NH 3. Note any of these unusual conditions in the logbook Checking and Setting Time On BUDL: Every 3-4 months, the PDL and BUDL times move apart and create a lag that slows down record keeping. If this occurs, follow the procedures in the ECB section to set the times together (within one minute of each other) Data Backup: Down load the data from the backup data logger (if applicable) twice per month on high density (HD) floppy diskettes. A backup is performed on the first of each month which contains data for the entire month previous. A backup is also done on the fifteenth of each month containing data from the first to the fifteenth of the present month. Send the previous month backup diskettes to the Data and Statistics Unit Supervisor at Raleigh Headquarters. The whole month of data diskette should be sent to and received by Headquarters no later than the 15th of the following month. Each time you download the data it may take 1-6 diskettes (3.5 inch diskettes)

22 Section Page 6 of 27 to contain the previous month s data. Another option is to download the data onto a zip disk and a copy of the data to wayne.cornelius@ncmail.net. If you experience any problems or complications with this downloading procedure, contact the Electronics and Calibration Unit for assistance. The procedure for downloading is as follows: BACKING UP FILES 1. Maximize the Digi Trend program window icon located on the taskbar at the bottom of the Windows desktop. 2. From the Digi Trend Main Menu select Utilities. 3. Scroll down and select Copy Files. 4. From the file menu choose items to be copied, normally Data Files. 5. Select Data type, normally Minute Data. 6. Select Time Options, use Range for middle and end of month and Month for entire month. If Range is selected, type in Start and End dates. Data will be backed up through the selected range of days. For example, if the range 01/01/01 to 01/15/01 is selected, data will be backed up for 01/01/01 through and including 01/15/ Note: It is very important to have a floppy disk in drive A: before you continue. 8. Select the Storage Drive: drive A: 9. Select Copy. 10. If more than one Floppy disk is needed, you will be prompted to insert another disk. Continue until no more disks are requested and the program is completed. Enter the following information on a label on each floppy disk: Disk Sequence No. 1 of 2; 2 of 2, etc. Site Name: e.g. Clinton Crops AIRS No.: e.g Parameters: NO X or NH 3 Month/Year of data recorded: MM/YY Your name: First and Last Name Date backup created: MM/DD/YY Within 10 days following the end of each month, forward each month s floppy disks to: Data and Statistics Branch Ambient Monitoring Section Mail Service Center 1641 Raleigh, NC

23 OPERATIONAL CHECKS Section Page 7 of 27 Conduct the following operational checks before running any unadjusted / adjusted checks. Record your observations in the logbook, do not make any adjustments during these checks. Phone ECB for guidance before making adjustments with the front panel pushbuttons. See section for a further description of the front panel pushbuttons "Power On" Check: verify the instrument "POWER" light is lit and there is an audible sound from the external pump. If instrument does not have any power, determine the cause and time of power failure. Invalidate data for the 20 minute period after the power comes back on. Correct the cause and verify zero and span. Record all events in logbook. Notify supervisor and the ECU Range Check: Select the Range Menu to verify that the range is at the correct setting of 200 ppb for the NO X and NH 3 channels. If the range has been changed, determine when and by whom. Invalidate all data in the wrong range. Notify supervisor and the Quality Assurance Coordinator immediately, conduct an unadjusted zero/span ( ), re-enter the range to the correct entry, then recalibrate. (Section ) Station Temperature Check: measure and record the site temperature in C. Adjust the site thermostats as necessary to maintain the 20 to 30 C range. If the temperature is outside of the 20 to 30 C range, notify the Regional Chemist and the ECB to correct the problem and invalidate data if necessary Vacuum Check: Select the Diagnostics > Pressure to read the reaction chamber vacuum gauge. Record value; do not adjust. If pressure alarm limits are exceeded, check for leaks, determine cause, correct accordingly, and record in instrument logbook Compressed Air Drying Column Replacement: Dry silica is blue, wet silica is white. Change the wet Silica gel in the compressed air drying column every week if necessary. Do not discard the wet silica gel - drying wet silica in a 120 C an oven until blue again regenerates it. Listen for any leaks due to loose fittings on the silica canisters. Record in logbook Capillary Replacement : If there is a problem in obtaining substantial NO X and NH 3 span levels, there maybe a problem with clogged capillaries. There are two capillaries for the SAMPLE and OZONE flows. Check sample and ozone flows by selecting Diagnostics > Flow. The sample flow should be checked on each of 3 cycles as a check for plugging capillaries. If the capillaries are plugged, the difference between the highest and lowest flows should be greater than 100ccm (0.1LPM). If greater than 100ccm (0.1LPM), replace sample flow capillaries according to the instructions in appendix at the back of this operator section. Sample flow capillaries are prone to plugging every 2-3 months and should be monitored routinely or every site visit. A plugged capillary is a system failure unadjusted calibrations before replacement are not required. Conduct an adjusted calibration after replacement Temperatures Select Diagnostics > Temperature and verify that the temperatures are within the following ranges: Internal: 20 C to 30 C. PMT cooler: 25 C to 1 C. Reaction chamber: C. NOx converter: 325 C to 350 C. NH 3 converter: 825 C.

24 Section Page 8 of Calibration Factors Select Diagnostics > Calibration Factors and record the before adjustment values of: Factor Normal Value Component NO bkg. less than 1.5 ppb NO x bkg. less than 1.5 ppb N t bkg. less than 1.5 ppb NO coef. near 1.00 NO x coef. near 1.00 NO 2 coef. 1 between and low temp. converter NO 2 coef. 2 between and high temp. converter N t bkg. near 1.00 NH 3 coef.1 close to zero low temp. converter NH 3 coef.2 close to 0.85 high temp. converter Maintenance and Troubleshooting Documentation Any other suspected mechanical problems see Section (ECB) for Preventative and Routine Maintenance or Appendix M for Troubleshooting. Document all of the above in the logbook Maintenance of Model 111 Zero Air Supply System: The exact life times of the scrubbing material is hard to predict. It is dependent upon flow, pressure, and level of contaminate. For most applications the following recommendations should be followed: WEEKLY: If optional automatic drain valve is not installed, open stop-cock on bottom of tank and drain water. MONTHLY: Check the condition of the Purafil. Fresh Purafil is purple. It becomes brown when it is used up. Replace when the purple color represents less than 20% of the volume. To replace, turn off power and unplug. Wait until reactor cools down. Remove the cartridge holding the Purafil. Unscrew cap, dump out used Purafil in a garbage bag and discard in the trash bin. Replace with fresh Purafil. Screw on cover and replace cartridge. YEARLY: Replace the charcoal. The procedure is the same as replacing Purafil, outlined in 1 above. PUMP: When it is observed that the pump is having difficulty keeping the pressure, Call ECB for replacement UNADJUSTED CALIBRATION A 4-Point NO x /NH 3 calibration and an NO 2 unadjusted check, including converter efficiency calculation (section ) is required every two weeks (14 days). Ensure proper operation of the 146C calibrator and the 17C analyzer according to If the NO x converter efficiency is < 96% or > 104%, recheck calculations and troubleshoot the analyzer. If converter efficiency remains low or high, contact the Electronics and Calibration Unit.

25 Section Page 9 of 27 Note: Do not perform checks or calibrations between 6:00 AM and 9:00AM "Local Standard Time". This is an important data collection period. LOGGING IN The following sequence is used to log onto the PDL and BUDL so that routine checks and calibrations may be conducted via the data logger. a) Turn on the screen and printer. b) Double click on Shortcut to Spltscrn icon located on the Windows 95 desktop. The PDL and BUDL Hyperterminal split screen windows appear. Note: To switch the cursor between the BUDL and PDL windows, press TAB with holding down ALT (ALT-TAB). When each window is selected, the top bar will be highlighted in blue. c) ALT-TAB to the BUDL (Back Up Data Logger) window. d) Press ESC, then type the two letter site code X X and "AQM" (with no spaces), press enter. This will get you on the backup data logger. Note: The two letter site code is a specific code for each site, contact the ECB for the two letter site code if necessary. e) Press "L" for "Login/set user level", (Note: It will ask for password but you enter the code), press Enter. Choose "C" (the Configuration Menu). Select "D" to configure the data channels. Press "M" to Disable/Mark (Down) Channel offline. Select NO x to select the NO x data and press Enter. Press "M" again and select NH 3 and press enter. Press ESC (slowly) until you reach Home Menu. f) To display the NO x and NH 3 channels, press "D" for Real Time Display and then "B" to display the Base Average in one minute readings with flags. g) ALT-TAB to the PDL (Primary Data Logger) window Note: Press ESC at any time to return to the > prompt on the PDL h) Press Alt "S" and type "E" to turn on printer (The printer will only operate when the printer buffer is full) or press Alt "T" to capture text to file. i) On the primary data logger type "!", and enter the 6-character password. At this point, you may select a number of reports that will provide information about the site operation. At a minimum, request "D", "Y", "2", and "F". j) Verify that the 146C Calibrator and the Model 111 Zero Air System is turned on. k) To down the NOx, NH 3 channels, type "#", enter the code, type 05, Press Enter, 08, Press Enter and Enter. Note: If you lose text while viewing the backup data logger screen, press the scroll lock key to the "ON" position and press the up arrow or "Page Up" key. Note: While enabling upping) or disabling (downing) the NO x and NH 3 channels, the scroll lock key must be in the "OFF" position to select the NO x and NH 3 channels. Note: While in the split screen system the printer will print when: 1) the printer buffer is full. 2) when you exit the split screen system

26 Section Page 10 of If the site has a CO monitor then set the CO autocal event well forward in time-- to prevent interruption of ongoing events during your visit. If site does not have a CO monitor, go to Note: Both CO and NH 3 monitors share the same 146C calibrator. An initial check of the events schedule should be performed first. The operator should first utilize the "N" command by pressing "N". This will display all events programmed in the primary data logger. Following the events review, the site operator should estimate the duration of site visit (i.e. take into account the type of visit activities deemed necessary-precision /zero /span, calibration, etc.). The operator must then advance the CO auto zero to a future odd hour to eliminate interruption of site activities; span, zero, calibration, etc. (Advance zero to future only). Setting the CO zero event: Once the site operator has pressed the "N" command and reviewed the auto zero, then the zero can be advanced. Type "+" and respond with the password or "Code". Respond to the questions shown below with the following: "Do you want to reset all events?" (Y/N) with N "Reset which event?" with 05 "Enable event 05?" with Y "Time of next event (HH:MM)=XX:46 "Date of next event (Mo/Dy)=current date "Frequency of event (DD:HH:MM)=00:02:00 "Duration of this event (HH:MM)=00:28 Change XX to an odd hour. Leave the :46 unchanged Hitting Enter Retains the current value. "Digital Output= This process results in starting the CO auto-zero at XX:46 (XX being the ODD hour), and to continue to run until the following even hour YY:14 (YY being the EVEN hour), resulting in a total zero of 28 minutes every 2 hours. This process skips an hour and then starts the 28 minute zero again. For example, if the operator begins at 01:00 (odd hour) the CO zero would follow a path such as this: 01: :14 (28 min. elapsed)>>>skip over until 03: :14 (28 min. elapsed)>>>skip over until 05: :14 and so on. Pushing this path forward to the future means that this path will restart from the odd hour where the operator advanced the CO auto zero. NOTE!! DO NOT ADVANCE THE AUTO ZERO (EVENT 05) TO BEGIN AT AN EVEN HOUR Anytime a site is started up or a cylinder / calibrator is changed, verify that the TEI Model 146C Calibrator s NO x and NH 3 Tank PPM is set to the same value as the NO x and NH 3 concentration of the on-site cylinders as follows: 1. While in Remote mode, hit the MENU pushbutton on the 146C until you bring up the Main Menu. 2. From the Main Menu, use the ENTER and pushbuttons to select Flow Controls > Automatic Settings > Gas A Dilution 3. Press ENTER to select or MENU to return to a previous menu if a mistake is made. 4. From Gas A Dilution select the Span 1 Parameter. 5. In the Span 1 Parameter screen, verify that the Tank PPM is set to the same value as NO X concentration of the on-site cylinder.

27 Section Page 11 of Hit MENU until you reach the main menu. 7. From the Main Menu, use the ENTER and pushbuttons to select Flow Controls > Automatic Settings > Gas B Dilution 8. Again, check the Span 1 parameter screen in Gas B Dilution, and verify that the NH 3 Tank PPM is set to match the on-site NH 3 cylinder. If the Tank PPM values do not match the on-site cylinders, phone ECB for guidance. Do not change any settings. If the Tank PPM and the NO X / NH 3 concentrations of the on-site cylinders match, then proceed to to begin the zero and start the unadjusted calibration. UNADJUSTED NO x /NH 3 ZERO Begin a Zero. Type "C", type the 6-character Access Code, press Enter to "Activate which events in a sequence?", then type "05" and press Enter for "Activate which event?". The NO x /NH 3 zero should begin. Press Enter when asked "Deactivate which Event" Press M, and for "view which columns?" type 06 and 08 press Enter. The data logger will display continuous one minute updates for NO x and NH 3 until ESC is pressed Recording the NO x /NH 3 zero Allow the Model 17C microprocessor to stabilize for at least 30 minutes, until the zero values are stable. Average and record five one-minute readings of NH 3 and NO x, in ppb, from the Primary and Backup Data Logger windows, into the logbook. UNADJUSTED NO x SPAN Start the NO x Span and Clear the Zero Mode. Press ESC. Type "C"in the PDL, enter the 6-character Access Code, press Enter for "Activate Which Events in Sequence?" and for "Activate Which Event?", type 06 and press Enter, then type "05" for "Deactivate which event?", and press Enter. The span should begin and the zero should stop Type "M" and type 06 and 08 and press Enter. After the monitor response has stabilized, review the next five one-minute averages on the printout. Mark the data logger values used on the printout To mathematically calculate the actual NO, NO x, N t, or NH 3 concentration (Ca) of approximately 90 % range of full scale (approximately 45 ppb, 90 ppb or 180 ppb), use the equations below: [NO] Ca = [F NO / (F NO + F ZERO )] [(NO std )] [NO x ] Ca = [F NO / (F NO + F ZERO )] [(NO std ) + (NO 2 ) imp ] [N t ] Ca = [F NO / (F NO + F ZERO )] [(NO std ) + (NO 2 ) imp ] Where: F NO + F ZERO = calibrated flows in sccm. [NO 2 ] imp = NO 2 impurity in cylinder (on certification sheet) [NO std ], [(NH 3 std )] = certified NO and NH 3 gas concentrations (on cylinders) Note: To convert liters to sccm, multiply liters by To convert ppm to ppb multiply by 1000.

28 Section Page 12 of After minutes, verify that the analyzer data logger has stabilized to obtain a level span trace. Verify that the display shows appropriate NOx concentrations. If not, press the "RUN" button until the NOx is displayed. Check that NO x are reading the ECB preprogrammed 146C values and the mathematically calculated NO x span value Average and record the last 5 minutes of averaged NO, NO x, N t readings from the analyzer front panel and NO x on the primary data logger and backup data logger readings in the instrument logbook. UNADJUSTED GAS PHASE TITRATION From the Gas A Dilution Run screen, record the zero air and gas flow necessary to produce the Span 1 output ppm NO 2 SPAN (Gas Phase Titration: for bi-weekly converter efficiency calculation) After recording the Span 1 Event (including the flows), start the Gas Phase Titration as follows: 1. While the Span 1 Event is still running, do the following: a. Press Enter to put the 146C in Local Mode. Note: Going to Local Mode WITHOUT a Remote event running could damage the 146C. b. Press MENU until you bring up the Main Menu. c. Select Flow Modes > GPT d. Change the GPT/GAS X prompt to GPT/GAS A using the arrows e. Press Enter to accept f. After the Saving Parameters prompt stops flashing, press Run. In the GPT Run screen, make sure you are at the option. If not, then press Run to scroll through all options (, Levels 2-5, and ZERO) until you arrive at the arrow option. Press ENTER to accept. Note: When there is a question mark (?) next to a setting, it means that the setting is inactive. If the question mark is removed, then the setting is active or live (the setting is what you are doing). g. Note your GPT zero air and GPT gas flows when you re running the GPT. If the flows are not exactly equal to the Span 1 zero air and gas flows that you recorded in , phone the ECB for guidance. 2. Once the GPT is running, use the arrows to adjust the O 3 LEVEL (percent ozonation) to 20%, press Enter to accept and allow readings to stabilize. The stabilized NO X readings should agree with the original NO X span value if the right amount of NO 2 is being converted to NO. Starting from 20% ozonation, slowly increase the O3 level until the NO readings drop to 10-20% of the span value (e.g. if the NO span is 90 ppb, increase the percent ozone level slowly until the monitor stabilizes at an NO reading of approximately 9-18 ppb). Usually, an O 3 level set between 20-30% accomplishes the required NO reduction. Once set, the O 3 level will work with other calibrations unless something changes such as a gas cylinder or an ozonator lamp. IMPORTANT: During the GPT, the NO reading must not be allowed to decrease by more than 90% of its original full scale span value (45 ppb for a 0-50 ppb range or 180 pbb for the ppb range) so that adequate NO is available for the NO/O 3 reaction and enough NO remains for accurate NO 2 calculations. If

29 Section Page 13 of 27 the NO reading drops by more then 90% (e.g. below 4.5 for a NO full scale span of 45 ppb), reduce the output of the calibrator until an acceptable NO reading is achieved Allow approximately 45 to 60 minutes for the NO 2 trace to stabilize. Verify the display is showing NO 2 concentration, pressing the "DISP' button to obtain "2". Note: The 146C will interrupt the Local Mode by automatically switching back to Remote after one-hour. To prevent this, press Run while in Local Mode to cycle through the options (, Levels 2-5, and ZERO) until you are back to the original option ( ) - the one you are running or the one without the "?" Calculate and record the resultant NO 2 logbook values using the following formula: [NO 2 ] Ca =[NO] orig -[NO] rem + D [NO 2 ] imp i.e. [NO 2 ] Ca = 180 ppb - 20 ppb +.7 ppb = ppb where: [NO 2 ] Ca = NO 2 concentration at the output manifold, ppb [NO] orig = original NO concentration before titration with O 3, ppb [NO] rem = NO concentration after titration with O 3, ppb [NO 2 ] imp = NO 2 impurity in cylinder NO 2 Impurity = NO x -NO values on certification sheets (i.e.,.7 ppm = 11.7 ppm ppm or 700 ppb = 11,700 ppb 11,000 ppb) F NO = NO flow rate, sccm F ZERO = Zero air flow rate, sccm (ozone flow rates included) D = Dilution ratio, F NO /(F NO +F ZERO ) Note: NO 2 impurity may be listed as an additional factor in certified Protocol NO gas received from the manufacturer. If so, this additional NO 2 must be included when calculating the total NO 2 concentration generated during gas phase titration. Note: To convert liters to sccm, multiply liters by To convert ppm to ppb multiply by After the appropriate time period, look for a stable NO 2 trace of about 10 minutes data logger duration Enter 5 minutes of averaged NO, NO x, N t, and NO 2 data logger and Backup data logger data into the calibration section of the logbook Document each point on the computer printout with the pollutant and calculated concentration for NO, NO x, N t, and NO 2. Complete the NO x and NO 2 zero/span page in the logbook Calculate converter efficiency for required biweekly checks as follows: %C.E. = { [NO 2 ] conv /[NO 2 ] Ca } 100 Where [NO 2 ] Ca = calculated concentration of NO 2 [NO 2 ] conv = [NO 2 ] Ca - ([NO x ] orig - [NO x ] rem ) [NO x ] orig = original concentration of NO x prior to addition of O 3, ppb [NO x ] rem = NO x concentration remaining after addition of O 3, ppb Record converter efficiency in the logbook. If converter efficiency is less than 96%, recheck calculations, and troubleshoot the instrument. If converter efficiency remains low, contact the Electronics and Calibration Unit.

30 When the titration finishes do the following: a. Press MENU b. Select Flow Modes c. From Flow Modes select Gas A Dilution d. Press Enter e. After the Savings Parameters prompt stops flashing, press Run Section Page 14 of 27 The 146C is now set-up to run the calibration points or the precision check. To cycle through the points press Run, to accept press Enter. CHECKING THE NO x CALIBRATION POINTS Generate a NO X calibration / precision point (as required) by pressing: 1. Press Run to scroll through the calibration points (Span 2 and Span 3): a. Span 2 = 50% full scale / calibration point b. Span 3 = 16% full scale / precision + calibration point 2. When desired calibration point is displayed on the 146C LCD, press Enter to activate. 3. Allow minutes for the readings to stabilize, record and average the last 5 data values. 4. Repeat steps 1-3 as necessary for the calibration 5. When the calibration is complete, press Run to scroll back to Span Press Enter to accept. 7. Press MENU until you bring up the Main Menu 8. From the Main Menu go to Flow Modes > Standby > Press Enter to put the 146C Local Mode in Standby. 9. Press Enter again to place the 146C back in Remote Mode, and proceed to to stop remote events. UNADJUSTED NH 3 SPAN Start the NH 3 Span and Clear the NO X span. Press ESC. Type "C", enter the 6-character Access Code, press Enter for "Activate Which Events in Sequence?" and for "Activate Which Event?", type 04 and press Enter, then type "06" for "Deactivate which event?", and press Enter. The NH 3 span should begin and the NO x span should stop Type "M" and type 06 and 08 and press Enter To mathematically calculate the actual NH 3 concentration (Ca) of approximately 90 % range of full scale (approximately 45 ppb, 90 ppb or 180 ppb), use the equations below: [NH 3 ] Ca = [F NO / (F NO + F ZERO )] [(NH 3 std )] Where: F NO + F ZERO = calibrated flows in sccm. [(NH 3 std )] = certified NH 3 gas concentrations (on cylinder) Note: To convert liters to sccm, multiply liters by To convert ppm to ppb multiply by 1000.

31 Section Page 15 of Wait approximately 90 minutes until the analyzer data logger has stabilized to obtain a level span trace. Verify that the display shows appropriate NH 3 concentrations. If not, press the RUN button until the NH 3 is displayed. Check that the NH 3 is reading the ECB pre-programmed 146C values and the mathematically calculated NH 3 span value Wait approximately 90 minutes until the monitor response has stabilized; average and record the next five one-minute averages on the printout. Mark the data logger values used on the printout. CHECKING THE NH 3 CALIBRATION POINTS Generate a NH 3 calibration / precision point (as required) by pressing: 1. Press Run to scroll through the calibration points (Span 2 and Span 3): a. Span 2 = 50% full scale / calibration point b. Span 3 = 16% full scale / precision + calibration point 2. When desired calibration point is displayed on the 146C LCD, press Enter to activate. 3. Allow minutes for the readings to stabilize, record and average the last 5 data values. 4. Repeat steps 1-3 as necessary for the calibration 5. When the calibration is complete, press Run to scroll back to Span Press Enter to accept. 7. Press MENU until you bring up the Main Menu 8. From the Main Menu go to Flow Modes > Standby > Press Enter to put the 146C Local Mode in Standby. 9. Press Enter again to place the 146C back in Remote Mode, and proceed to to stop remote events. 10. Deactivate the NH 3 span DATA ANALYSIS For each concentration, calculate the NO X and NH 3 concentration and record the analyzer's response (PDL and BUDL). Compare the calculated or True values of the NO x and NH 3 calibration/precision points to the corresponding PDL and BUDL values. All calibration points must meet the following criteria: Percent Tolerances across all fullscale (FS) ranges (50, 100, 200) Point Unadjusted Adjusted Tolerance Tolerance Span(90%) ±10% ±8% Mid(50%) ±10% ±8% Precision(16%) ±15% ±12% zero(0) ±5ppb ±3ppb NO 2 span ±5% ±5% Nominal or designated value of each point % Difference = 100 (measured actual)/actual If any of the points are greater than the unadjusted tolerance for the fullscale range, the unadjusted calibration is unacceptable and an adjusted calibration is required according to procedures in If the span differs by ±25% or more from theoretical, invalidate the data collected since the last acceptable check and perform all checks and corrective actions identified

32 Section Page 16 of 27 by , follow the Troubleshooting Guide in Appendix M, and recalibrate. If the adjusted calibration is unacceptable after two tries, contact the ECB. All points on an adjusted calibration must meet their respective adjusted tolerance criteria. Adjustments to the 17C should be based on the 17C not meeting the tolerance criteria. Needless adjustments could damage the 17C If the unadjusted calibration is acceptable, proceed to document the operational checks in section and then logout as in If the unadjusted calibration is not acceptable, conduct and document the operational checks in before proceeding to Section for an adjusted calibration ADJUSTED ZERO/SPAN CHECKS / CALIBRATIONS Significant drift is not expected with the digital Model 17C microprocessor such as with analog systems; however, adjustments to zero and span potentiometers are applicable. An adjusted calibration according to Section should be performed if any points have an error (percent difference) of > 10% from the actual concentration Label the printout to indicate the site name and operator's name performing site checks. ADJUSTING THE ZERO Begin a zero by typing "C", entering the 6-character Access Code, pressing the Enter key for "Activate which events in sequence?", then by typing "05" for "Activate which event?" The zero should begin. Type "M" then type 06, 08 in succession and Enter to display the one-minute updates Select the Range Menu to verify that the range is at the correct setting (check with QA coordinator if not sure) for the NO X and NH 3 channels Setting NO x and NH 3 Zero Allow the Model 17C microprocessor to stabilize for at least one hour, until the zero channels on the data logger are stable. After waiting, adjust the 17C zero as follows: 1. Press MENU on the front panel of the 17C Analyzer to select Main Menu. 2. Choose Calibration from the Main Menu using the arrows. Press ENTER to select. 3. From the Calibration Menu choose Calibrate Zero and press ENTER to select. 4. At the Set to Zero prompt, press ENTER. 5. Wait until the Savings Parameters prompt stops flashing. 6. Press MENU twice to return to the Main Menu. Wait a minimum of 10 minutes for the microprocessor to stabilize. The microprocessor will calculate, apply and store the zero background corrections, {NO bkg., NO x bkg., N t bkg (all in ppb)} for all four channels. Enter 5 minutes of averaged NO x and NH 3 data logger data in the logbook (see Appendix B.2). The data logger and backup data logger should read 0±2 ppb for NO x and NH 3 on the terminal printout. If NO x and NH 3 channels are not in this range, contact the ECB.

33 ADJUSTING THE NO x SPAN Section Page 17 of Setting NO x Span Press ESC. Clear the zero mode by typing "C", entering the 6-character Access Code, pressing the Enter key for "Activate which events in sequence?" and for "Activate which event?" type "06", then type "05" for "Deactivate which event?". The NO x span should begin and the zero should stop. Type "M" then type 06, 08 and Enter to display the one-minute updates Calculate actual NO, NO x, and N t concentrations (Ca) of approximately 90 % of fullscale range (approximately 45 ppb or 180 ppb) using the equations below. Record the NOx span in the logbook. [NO] Ca = [F NO / (F NO + F ZERO )] [(NO std )] [NO x ] Ca = [F NO / (F NO + F ZERO )] [(NO std ) + (NO 2 ) imp ] [N t ] Ca = [F NO / (F NO + F ZERO )] [(NO std ) + (NO 2 ) imp ] Where: F NO + F ZERO = calibrated flows in sccm. [NO 2 ] imp = NO 2 impurity in cylinder (on certification sheet) [NO std ], [(NH 3 std )] = certified NO and NH 3 gas concentrations (on cylinders) Note: Multiply liters by 1000 to convert to sccm; multiply ppm by 1000 to convert to ppb. i.e., if [NO] std = 5.44 ppm, F NO = sccm and F ZERO = 9797 sccm (9.797 lpm), then NO]= ppm (44.05ppb) After at least minutes, verify that the analyzer data logger has stabilized to obtain a level span trace. Verify that the 17C display shows appropriate NO, NO x and N t concentrations. If not, choose MENU > Calibration Menu > Calibrate Zero and press ENTER to see NO, NO x and N t displayed on the 17C front panel. After stabilization of all three channels, follow the procedure below to set the NO x span: 1. Press the MENU button on the 17C Analyzer until you bring up the Main Menu. 2. Using the arrows, choose the Calibration Menu. Press ENTER to select. 3. Choose Calibrate NO and press ENTER to select. 4. Using the arrows to move the cursor left and right and the arrows to set the digits, enter the calculated NO span concentration, NO Ca, at the SET NO TO ? prompt. 5. Change the display to NO x through the Calibration Menu and repeat this procedure to enter the calculated NO x concentration, NO x ca, at the SET NOX TO prompt. 6. Also repeat this procedure to enter the N t (total nitrogen) span using the NO x ca value as the N t span concentration at the SET Nt TO ? prompt. 7. Wait an additional 10 minutes for the microprocessor to stabilize, repeating all entries, if necessary. Check that NO, NO x, and N t displays are reading the calculated NO ca and NO x ca spans. If you cannot obtain the appropriate NO x span readings on the data logger and backup data logger, troubleshoot the instrument according to Appendix M. If no problem can be detected, the instrument may be malfunctioning. Call the Electronics and Calibration Branch.

34 Section Page 18 of Record the last 5 minutes of averaged NO, NO x, and N t front panel and back-up data logger data in the calibration form of the instrument logbook. ADJUSTING THE NO 2 SPAN NO 2 adjusted span with Gas Phase Titration (for determining converter efficiency only). After adjusting the NO, NO x, and N t span point, follow the procedure below to start the Gas Phase Titration. While the NO x Span 1 Event is still running: 1. Press Enter to switch the 146C into LOCAL mode 2. Press the Menu Button 3. Select Flow Modes and press Enter 4. Select GPT, press Enter 5. Select GAS A from the SET GPT/GAS X prompt, press Enter 6. After the Saving Parameters prompt stops flashing, press Run IMPORTANT: During the GPT, the NO reading must not be allowed to decrease by more than 90% of its original full scale span value (45 ppb for a 0-50 ppb range or 180 pbb for the ppb range) so that adequate NO is available for the NO/O 3 reaction and enough NO remains for accurate NO 2 calculations. If the NO reading drops by more then 90% (e.g. below 4.5 for a NO full scale span of 45 ppb), reduce the output of the calibrator until an acceptable NO reading is achieved While waiting approximately 45 to 60 minutes for the NO 2 trace to stabilize, verify the display is showing NO 2 concentration, pressing the "RUN" button to obtain the NO After the appropriate time period, look for a stable NO 2 trace of about 10 minutes data logger duration. Calculate the actual concentration of the NO 2 span using the equations below. (Obtain values of NO, NO x, and N t from the Calibrate Zero Menu). Wait until the actual concentration is on the data logger. [NO 2 ] Ca = [NO] orig - [NO] rem + D [NO 2 ] imp i.e. [NO 2 ] Ca = 180 ppb - 20 ppb +.7 ppb = ppb where: [NO 2 ] Ca = NO 2 concentration at the output manifold, ppb [NO] orig = original NO concentration before titration with O 3, ppb [NO] rem = NO concentration after titration with O 3, ppb [NO 2 ] imp = NO 2 impurity in cylinder NO 2 Impurity = NO x -NO values on certification sheets (i.e.,.7 ppm = 11.7 ppm ppm or 700 ppb = 11,700 ppb 11,000 ppb) F NO = NO flow rate, sccm F ZERO = Zero air flow rate, sccm (ozone flow rates included) D = Dilution Ratio, F NO /(F NO +F ZERO ) Note: NO 2 impurity may be listed as an additional factor in certified Protocol NO gas received from the manufacturer. If so, this additional NO 2 must be included when calculating the total NO 2 concentration generated during gas phase titration. Note: To convert liters to sccm, multiply liters by To convert ppm to ppb multiply ppm by Set the instrument display to read NO 2 and adjust the NO 2 channel as follows: 1. Press the MENU button on the 17C Analyzer until you bring up the Main Menu. 2. Using the arrows, choose the Calibration Menu. Press ENTER to select.

35 Section Page 19 of Choose Calibrate NO2 and press ENTER to select. 4. Using the arrows to move the cursor left and right and the arrows to set the digits, enter the calculated NO 2 span concentration, NO 2 Ca, at the SET NO2 TO ? prompt. 5. Press ENTER. Wait until the Savings Parameters prompt stops flashing. Wait for the microprocessor to stabilize, and enter 5 minutes averaged NO 2 data logger and backup data logger data into the calibration section of the logbook. If the NO 2 channel is adjusted, recheck the NO and NO x span values, and readjust if necessary Record and average 5 minutes of averaged NO, NO x, and N t data from the 17C front panel into the calibration logbook. Record and average the NO 2 front panel data into the calibration logbook When the titration finishes do the following: a. Press MENU b. Select FLOW MODES c. From FLOW MODES select GAS A DILUTION d. Press Enter e. After the Savings Parameters prompt stops flashing, press Run The 146C is now set-up to run the calibration points or the precision check. To cycle through the points press Run, to accept press Enter. CHECKING THE NO x CALIBRATION NO/NO x Precision Points: see Section for more detailed information Generate an NO/NO x calibration / precision points (as required) by pressing: 1. Press Run to scroll through the calibration points (Span 2 and Span 3): a. Span 2 = 50% full scale / calibration point b. Span 3 = 16% full scale / precision + calibration point 2. When desired calibration point is displayed on the 146C LCD, press Enter to activate. 3. Allow minutes for the readings to stabilize, record and average the last 5 data values. 4. Repeat steps 1-3 as necessary for the calibration 5. When the calibration is complete, press Run to scroll back to Span Press Enter to accept. 7. Press MENU until you bring up the Main Menu 8. From the Main Menu go to Flow Modes > Standby > Press Enter to put the 146C Local Mode in Standby. 9. Press Enter again to place the 146C back in Remote Mode, and proceed to to stop remote events Stop the NOx span mode. Press ESC, enter "C", the six character code, and press Enter to "Activate Which Events in sequence" and "Activate Which Events". Answer "06" to "Deactivate Which Event" and press Enter.

36 Section Page 20 of Record the requested data in the logbook, including the ending pre-reactor zero background (b0), NO zero background (b1), NO x zero background (b3), NO Span Factor (S.F.) and NO y Balance Factor (b.f.) by activating the STAT pushbutton to actuation 6 and recording options 10, 11, 12, 13, and 14 as described in section f If the adjusted calibration is unacceptable in that it does not meet the adjusted tolerance criteria in section for each point, rerun the adjusted calibration including the NO 2 span according to the procedures in If the adjusted calibration is acceptable then complete and logout following the procedures in Document each point on the strip chart with the pollutant and calculated concentration, also DL value for NO x and NH 3. Complete the NO x and NH 3 precision/span page in the logbook Calculate converter efficiency as follows: %C.E. = ( [NO 2 ] conv / [NO 2 ] Ca ) 100 Where [NO 2 ] Ca = calculated concentration of NO 2 [NO 2 ] conv = [NO 2 ] Ca - ([NO x ] orig - [NO x ] rem ) [NO x ] orig = original concentration of NO x prior to addition of O 3, ppb [NO x ] rem = NO x concentration remaining after addition of O 3, ppb Record converter efficiency in the logbook. If converter efficiency is <96% or >104%, recheck calculations, and troubleshoot the instrument. If converter efficiency remains low, contact the Electronics and Calibration Unit. ADJUSTED NH 3 SPAN Start the NH 3 Span and Clear the NO X span. Press ESC. Type "C", enter the 6-character Access Code, press Enter for "Activate Which Events in Sequence?" and for "Activate Which Event?", type 04 and press Enter. The NH 3 span should begin Type "M" and type 06 and 08 and press Enter To mathematically calculate the actual NH 3 concentration (Ca) of approximately 90 % range of full scale (approximately 45 ppb, 90 ppb or 180 ppb), use the equations below: [NH 3 ] Ca = [F NO / (F NO + F ZERO )] [(NH 3 std )] Where: F NO + F ZERO = calibrated flows in sccm. [(NH 3 std )] = certified NH 3 gas concentrations (on cylinder) Note: To convert liters to sccm, multiply liters by To convert ppm to ppb multiply by Wait approximately 90 minutes until the analyzer data logger has stabilized to obtain a level span trace. Verify that the display shows appropriate NH 3 concentrations. If not, press the RUN button until the NH 3 is displayed. Check that the NH 3 is reading the ECB pre-programmed 146C values and the mathematically calculated NH 3 span value.

37 Section Page 21 of Wait approximately 90 minutes until the monitor response has stabilized; average and record the next five one-minute averages on the printout. Mark the data logger values used on the printout. CHECKING THE NH 3 CALIBRATION POINTS Generate a NH 3 calibration / precision point (as required) by pressing: 1. Press MENU on the front panel of the Model 146C Calibrator to select the Main Menu 2. Using the arrows, select Flow Modes and press ENTER. 3. In Flow Modes, select Gas B Dilution. Press ENTER. 4. After the Savings Parameters prompt stops flashing, press RUN. 5. Press RUN to scroll through the calibration points (Span 2 and Span 3): Span 2 = 50% full scale / calibration point Span 3 = 16% full scale / precision + calibration point 6. When desired calibration point is displayed on the 146C LCD, press Enter to activate. 7. Allow minutes for the readings to stabilize, record and average the last 5 data values. 8. Repeat steps 1-3 as necessary for the calibration 9. When the calibration is complete, press Run to scroll back to Span Press Enter to accept. 11. Press MENU until you bring up the Main Menu 12. From the Main Menu go to Flow Modes > Standby > Press Enter to put the 146C Local Mode in Standby. 13. Press Enter again to place the 146C back in Remote Mode, and proceed to to stop remote events. 14. Deactivate the NH 3 span LOGGING OUT If this site is equipped with a CO monitor then, verify the CO bi-hourly auto zero as follows if no further checks are planned, otherwise go to Make sure that the bi-hourly CO zero will be activated at the next available ODD hour (XX:46). Enter the password, type + and enter the code. Respond to the question shown below with the following: ENABLE EVENT 05? with Y TIME OF NEXT EVENT (HH:MM) = XX:46 DATE OF NEXT EVENT (MO/DY)= CURRENT DATE FREQUENCY OF EVENT (DD:HH:MM) = 00:02:00 DURATION OF THIS EVENT (HH:MM) = 00:28 DIGITAL OUTPUT = EVENT START FREQUENCY DURATION DIGITAL OUTPUT # TIME DD:HH:MM HH:MM 5 13:46 00:02:00 00: Wait approximately five minutes for the PDL to stabilize at ambient values, then enable (Up) the primary data logger NO x and NH 3 channels as follows: Press U and enter "06" to "up the column number" and press Enter and repeat for the "08" column. Press Enter again to exit to the cursor. Type "M" to view columns "06" and "08". When all the flags have cleared, type "!" to exit the PDL. Record the time at which you upped the PDL channels in the logbook.

38 Section Page 22 of The theoretical span value will already be programmed in the data logger by the ECB. However, if the actual span concentration from the 146C calibrator has been changed, change the "Theoretical Span Value" by pressing "G", entering the code, the NO x channel number, and pressing "Enter" to each question until "Theoretical Span Value=" is printed out. Respond by typing in the new span concentration in ppb, press Enter, and then Esc. Repeat for the NH 3 channel number Enable (Up) the backup data logger NO x and NH 3 channels as follows: Go to the Home Menu (by pressing "Esc" several times (slowly) if needed), choose "C" (the Configuration Menu). Select "D" to configure the data channels. Press "E" to Enable/Mark Channel online. Select NO x to up the NO x channel and press Enter. Press "E" again to Enable/Mark Channel online, and select the NH 3 to up the NH 3 channel. When finished, exit to the "Home Menu", by pressing ESC and ESC, (slowly). Verify the flags are cleared and the channel is enabled by pressing "D" and then "B". If the flags are cleared, press "Esc" and "Esc" to go back to the home menu, press "O" to Log out. Note: Allow several data updates for the flags to disappear on the BUDL channels after enabling the NO x and NH 3 channels To exit the split screen operation (remember to logout of the PDL and BUDL before exiting split-screen): -- close both the PDL and BUDL windows after upping the channels and logging out. Click yes when asked if you want to disconnect now? The Digi-Trend Poll Manager will automatically begin polling for the previous data. Maximize the Digi-Trend Poll Mangager to see how the polling is progressing. Polling can last minutes or longer depending on when the last poll occurred. After the polling finishes, do not close the Digi-Trend Main Menu screen, minimize it to leave it active after you leave the site If experiencing difficulties, manually poll the BUDL to flag, print, and review the data as follows: On the ESC menu, move the arrow to Utilities and select Manual Poll, and press Enter. Press Tab and enter the date and hour on which you started the check (when you downed the channel). Also, enter the ending date and current hour, and press Enter. Type Y for Are Dates OK? [Y/N] Flag Data with a Chart Stamp Memo: When the Polling finishes proceed as follows: Double click the Graph Icon on the DigiTrends screen. Click on the site name. Highlight the NO x parameter from the list of parameters to graph and click OK. Choose one-minute historical data to graph in Engineering Units. Choose the Beginning Graph Date and Hour: MM/DD/YY/HH by clicking on the calendar window and 00. Choose the number of hours to display (on graph) on one screen: (1, 3, 6, 12, and 24 hours). Press Load Data. 1. To enter a memo on a strip chart graph: Click the exact point on a trace, by scrolling with the > or < buttons, where you want the memo to be attached. Clicking the exact point may be difficult to do. Try to select a point near the intended point if unable to select the intended point. That selected data point will then be displayed as a small square on the trace. Remember to find a point near the intended point. 2. Hold down the Shift key on the keyboard and click the left mouse button on that data point again.

39 Section Page 23 of A blank memo screen will appear. Type the memo in the text box near the bottom of the screen. Click OK to save the memo or click Cancel to discard it. You will return to the graph display. (Note: Saved memos cannot be altered or deleted. Press the refresh button on the Graphing software toolbar if memos don t appear on screen when viewing a previously documented graph). Use the procedure 1-3 above to place the following three memos on the trace for both unadjusted and adjusted calibrations as necessary: = = Find the place in the graph where you started the unadjusted (or adjusted) Precision/Zero/Span Check or calibration (downed channels). Document in the text box section Beginning of (unadjusted checks / adjusted checks) and any other pertinent information. Find the place in the graph where you placed the monitor back in service (upped the channels to collect ambient data). Place a finishing memo at that point. Document in the text box section End of (adjusted checks / unadjusted checks) and any other pertinent information. On the graph, the memos inserted above will look like large dots. To open and review the information in a previous memo or add additional comments for the same memo point, click the mouse pointer on the large dot representing the memo you want to open. Hold down the Shift key and click the left mouse button again. Scrolling Features: The > or < buttons allow you to scroll forward and backward in time (along the x-axis). For example, if one-hour data is being graphed and the Scrolling Interval is set to three, the graph will scroll forward in three minute intervals each time the > button is clicked or backward three minutes each time the < button is clicked. To select a scrolling interval, click the down arrow for a drop-down list. Interval choices are 1, 3, 6, 12, and 24. The default is 1 interval Repeat steps for the NH 3 channel On the ESC menu screen Close the chart screen and maximize the DigiTrends Screen. The ESC Main Menu should appear. Check the next autopoll time on this screen. The autopoll time should occur at the next odd hour from the current computer time. If this time is not correct, contact the ECB. Turn off the computer screen DATA ACQUISITION DATA REPORTING FOR REGIONAL OFFICES Automatic Data Reduction Procedures When the primary data logger has been shown to be obtaining acceptable data, the data will be automatically collected by the Headquarters computer using polling routines. The actions required by the regional staff are to report reasons for missing data; identify invalid data; identify data to be changed by headquarters; calibrate ( ) the monitoring system; validate the data ( ); and audit the monitor performance ( ).

40 Section Page 24 of The site operator must account for all periods of missing or invalid data. Identify the reasons for missing or invalid data on an AQ-42, in remarks Any invalid data reported by the data logger as "valid" data must be listed on an AQ-42 for editing (deletion) by headquarters Any valid data identified by the data logger as "invalid" data (by flags) must be reported manually on an AQ-42 for entry by headquarters Any remarks or comments about the data must be reported on a AQ When data logger data does not meet the acceptance criteria in , the data must be reported manually on an AQ Manual Data Reduction Procedures High sensitivity NO x and NH 3 analyzer data will be stored on the primary data logger and on the BUDL. The operator is responsible for assuring that as much valid hourly data is reported as possible. When the primary data logger does not collect data or the data is invalid for a reason related to the primary data logger, the operator should report the data from the BUDL minute data diskettes Generally, the least efficient way of providing hourly data from the BUDL is to manually calculate the hourly averages. Manual calculation will be a time consuming process. It may be efficient if only one or two hours of data per day needs to be taken from the BUDL. The hour XX:00 includes the starting at XX:00 through XX:59 (ie.,05:00 is the average of 05:00 through 05:59). Calculate each hourly average from the minute values using the equation: Hour Avg U = [ (m 1...m n ) ] / n where m = each valid minute value n = the minutes of the hour to compute a valid hour n 45 ( there must be 45 or more minutes in the hour) Headquarters' software has this capability of determining hourly averages from the minute data. If more than a few hours of data need to be obtained from the minute data (BUDL), then notify headquarters to do this on an AQ-42 by marking the candidate hours as "Recover." All data must represent Eastern Standard Time. During Daylight Savings Time, EST is equal to EDT minus one hour Report the average on the AQ-42 at the start of the hour (1:00-2:00 is reported as 1:00) Only one month should be entered on an AQ-42. Begin each new month on a new AQ Each AQ-42 must be labeled to show site identification number, time interval, the dates, and the remarks All data should be submitted to headquarters within 10 days from the end of the collection month and must be submitted within 15 days.

41 Section Page 25 of All data, including logbooks & computer printouts, must be kept for five years DATA VALIDATION FOR REGIONAL OFFICES The regional office is responsible for data validity Data Reported Manually The operator must review all AQ-42s for unusually high or low concentrations. Mark "DV" in the upper right hand corner for all one hour values exceeding the range of the monitor for NO x and NH For the 17C analyzer, zero concentrations may be reported. The 17C analyzer has a minimum detectable level of 1 ppb If an auditor receives data not within the criteria, then evaluate both the operator's readings and averaged readings to determine the cause of the differences The auditor signs, dates, and submits the completed AQ-42s to the data technician in Raleigh Headquarters Data Reported Automatically The operator must review all data submitted by the data logger. This is done primarily by reviewing printouts created by site calls ( ) and site visits ( ). Any unusual high (>_ 50 ppb) or low data (.000 ppb), data with invalidation flags, or missing data must be given special review When requested, provide photocopies of the primary or BUDL printout and logbook pages. The photocopies must show (1) prior calibration, (2) prior manual zero, precision, and span checks, (3) subsequent manual zero, precision, and span checks, (4) prior auto zero and span check (record the theoretical auto span value), and (5) the exceedance. Complete the AQ-124, keep a copy of the report, and send the original to the headquarter's Data Technician within two weeks of receipt of a request for the information For Flagged data, verify the flags are appropriate and note your findings on the terminal printouts. Note: Use of the Monthly File Listing for the checks below is preferred Verify that any valid data identified by the data logger as "invalid" data (by flags) have been reported manually on a Monthly File Listing or on an AQ-42 for entry by headquarters, or the candidate hours have been marked on an AQ-42 with the word "Recover" for hours that may be recovered from the one-minute data files. If there are just a few hours, the region can calculate the hourly averages from the minute data as follows: Hour Avg U = [ (m 1...m n ) ] / n where m = each valid minute value n = the minutes of the hour to compute a valid hour n 45 (there must be 45 or more minutes in the hour)

42 Section Page 26 of Verify that any invalid data reported by the data logger as "valid" data have been marked out on a Monthly File Listing or listed on an AQ-42 for editing (deletion) by headquarters Verify and account for all periods of missing or invalid data. Identify reasons for missing or invalid data on the Monthly File Listing or on an AQ-42 in the "REMARKS" section QUALITY ASSURANCE PROCEDURES A flow diagram for continuous ammonia monitoring is shown in Figure The Quality Assurance Program involves running audits to determine statistically the accuracy, precision, and thus, the reliability of the total set of data. Certain data must be available to the auditor. Use a Data Assessment Report (AQ-98) to report the results of each audit PROCEDURES FOR THE OPERATOR (MONITORING TECHNICIAN) The major part of the monitoring technician's role in the Quality Assurance Program is the carrying out of his duties in accordance with the preceding operating procedures and performing the following duties: Precision Auditing Every two weeks (14 days), conduct a zero, span, mid, and a one-point 16% of full scale precision check for NO x and NH 3 and a span check for the NO 2 channel (GPT, required for determining converter efficiency). Make no monitor adjustments prior to the precision check. The GPT check may be done in conjunction with a NO x and NH 3 zero/span check (see Section ) Calculate the average precision value readings for the NO x and NH 3 channels Save the printout showing the precision check results by stapling the printout to the logbook page PROCEDURES FOR THE REGIONAL AUDITOR Scheduling The auditor should verify that all precision checks are conducted as required by Accuracy Auditing The auditor should assist the Headquarters auditor in conducting quarterly accuracy audits, if requested Precision Audit Calculations Obtain the AQ-98 Data Assessment Report from the operator. Inspect and verify that the AQ-98 Data Assessment Report is complete.

43 Section Page 27 of 27 _ Calculate each instrument's quarterly average precision difference, d 1, as follows: _ d 1 = [ d 1j ]/j where: = average precision percentage difference at a monitoring site (as oppose to d 2 which is the d 1 j percentage difference for accuracy) per calendar quarter. = the number of precision checks performed at a monitoring site per quarter. j = 6 or 7 if precision checks are conducted twice every month. d 1j = the precision percent difference for the j-th precision check at a monitoring site. _ Report all d 1 values on the AQ-98 Data Assessment Report. (See Appendix B.1.) Audit Evaluation and Corrective Action An investigation must be undertaken in order to determine the cause of unusually poor audit results when any d 1j or d 2j exceeds +_ 25 % difference. Corrective action must be taken and documented. The regional auditor must initiate zero/span checks ( ), troubleshooting (Appendix Sec. M), recalibration ( ), and/or data validation / invalidation Data Verification The regional auditor must conduct the verification activities in Systems Auditing The auditor must participate in the annual systems audit and should complete any systems audit forms provided by the QAC PREPARATION OF THE DATA ASSESSMENT REPORTS (REGIONAL OPERATORS) Regional operators will complete the AQ-98 Data Assessment Reports, which contain monitor precision check information. Is 17C NH 3 span>10% out? YES NO has it been 14 days since your last precision check? YES NO No further action required Perform an on-site precision check: U Z NOX S NOX GPT NOX 50% 16% U Z NH3 S NH3 n/a 50% 16% Document the reason for 17C being out.(section ). Perform unadjusted and/or adjusted calibrations on-site as required: U/A Z NOX S NOX GPT NOX 50% 16% U/A Z NH3 S NH3 n/a 50% 16% Did the adjusted calibration bring the instrument back within the limits set forth in this QA (section )? YES NO Perform a 2 nd adjusted calibration. If 2 nd calibration fails, contact the ECB. Document the adjusted calibration in the logbook and electronically on the site computer (section ). Get the computer printout (soft copy is ok) as a record of your site visit and file it. Figure : Flowchart of Continuous NH 3 Monitoring

44 Appendices Appendix B.1: AQ-98

45 Unadjusted NO X Calibration C a (PPB) C m (PPB) Calibration %Diff Points Flow Gas Flow Air PDL BUDL PDL BUDL 146C LCD 146C LCD NO NO X N t NO NO X N t NO NO X N t NO NO X N t NO NO X N t 0 45 / 90 / / 50 / / 16 / 32 Unadjusted NH 3 Calibration C a C m (PPB) %Diff Channels down (Enter Time): Calibration Points Flow Gas Flow Air PDL BUDL PDL BUDL Channels uppped (Enter Time): 146C LCD 146C LCD NH 3 NH 3 NH 3 NH 3 NH 3 146C Tank Conc. readout PPM 0 Site Tank Conc. PPM 45 / 90 / / 50 / 100 Factors (no adjustments made): 8 / 16 / 32 NO bkg. Accuracy Criteria for unadjusted (UCAL) NO x bkg. and adjusted (ACAL) calibrations: N t bkg. 17C C a UCAL ACAL NO coef. zero ±5ppb ±3ppb NO x coef span ±10% ±8% NO 2 coef2 mid ±10% ±8% N t coef precision ±15% ±12% NH 3 coef 1 Adjusted NO X Calibration Calibration Points 0 45 / 90 / / 50 / / 16 / 32 NH 3 coef 2 C a (PPB) C m (PPB) %Diff Flow Gas Flow Air PDL BUDL PDL BUDL 146C LCD 146C LCD NO NO X N t NO NO X N t NO NO X N t NO NO X N t NO NO X N t Adjusted NH 3 Calibration C a C m (PPB) %Diff Factors after adjustments made: Calibration Points Flow Gas Flow Air PDL BUDL PDL BUDL NO bkg. 146C LCD 146C LCD NH 3 NH 3 NH 3 NH 3 NH 3 NO x bkg. 0 N t bkg. 45 / 90 / 180 NO coef. 25 / 50 / 100 NO x coef 8 / 16 / 32 NO 2 coef2 N t coef 1. Is UCAL calibration acceptable? Yes No NH 3 coef 1 2. If UCAL is outside criteria, perform an adjusted calibration (ACAL). NH 3 coef 2 3. If done, is ACAL acceptable? Yes No 4. If ACAL is unacceptable, troubleshoot the instrument, perform 2nd ACAL. 5. If 2nd ACAL fails, contact the ECB. Appendix B.2: Logbook and Operational Test Form

46 NH3 /NOX GENERAL CHECKS: MODEL 17C CIRCLE RANGE: 0-50 PPB PPB PPB Date: Time: Operator: Next O/SC Due: Next CalDue: Manifold Flow Y N Action Inlet Clean Y N Action Site Temperature (20/30 o C) A/C-Heater Operate Y N Action NO Cylinder Expires (date) Cylinder Pressure psi Cylinder Number Power ON: Model 17C ZAP Compressors PDL BUDL ANALYZER: Range:NH3 NOX Temperatures: Internal Chamber Capillary Cooler NOx.Converter NOx Converter set NH3 Converter NH3 Converter set Pressure Flows: 1. Ozonator 2.Sample Flow (low cycle) 3.Sample Flow (high cycle) flow (3 subtract 2) (>.1 is bad!) Zero Pak Silica Gel Changed Y N Date Sample flow capillaries changed Y N Date DATALOGGERS: Datalogger Type: BUD Type: Datalogger up? Y N Action Time Adjust? Y N Action Diskette downloaded and removed? Y N Date MODEL 111 ZERO AIR SYSTEM: Purafil changed Y N Date Charcoal Y N Date Final Pressure Regulator psi Y N Action Compressor Pressures: psi Y N Action psi Y N Action Drain Valve released (Weekly) Date Rotameter 1-2 Lpm Y N Action Comments NO 2 Ca (PPB) = NO Cm (DL span) NO rem + [F gas/(f gas + F zero)] x [NO 2 cyl. Conc. (ppm) x 1000] U GPT O 3 Level NO rem NO X rem NO 2 Cm % Diff NO 2 Imp NO 2 Ca 50/100/200 % PDL BUDL PDL BUDL PDL BUDL PDL BUDL Is 96% Converter Efficiency 104%? Yes No If No, do an adjusted NO/NOy/ NO2 calibration If Yes, Calibration Acceptable NO 2 Ca (PPB) = NO Cm (DL span) NO rem + [F gas/(f gas + F zero)] x [NO 2 cyl. Conc. (ppm) x 1000] A GPT O 3 Level NO rem NO X rem NO 2 Cm % Diff NO 2 Imp NO 2 Ca 50/100/200 % PDL BUDL PDL BUDL PDL BUDL PDL BUDL Is 96% Converter Efficiency 104%? Yes No If No, do an adjusted NO/NOy/ NO2 calibration If Yes, Calibration Acceptable Model 17C CONVERTER EFFICIENCY: NO, Point 50/100/200 N02 (Ca) NOX orig DL (ppb) U GPT A GPT NO2 Conv = [NO2 Ca - (NOX orig -NOX rem) ] NOX rem DL (ppb) N02 CONV (ppb) % C.E. Converter Efficiency = ([NO2]conv/ [N02]Ca) X 100 {~96.0%} Is Converter Efficiency greater than 96%? Y N Action C.E. 17C Panel % Appendix B.2: Logbook and Operational Test Form

47 A. INSPECTION AND REPLACEMENT OF CAPILLARIES Converter Module The following procedure should be performed every three months. 1. Turn the instrument off and unplug the power cord. 2. Remove the cover of the converter module. 3. Locate the heated capillary holder (see Figure 7-3). 4. Remove the Cajon fitting(s) from the reaction chamber body using a 5/8" wrench. 5. Remove the glass capillary(s) (part no. 4121) and O-ring (part no. 4800). Inspect O-ring for cuts or abrasion. If cut or abraded, replace. [See Figure a] 6. Check capillary for particulate deposits. Clean or replace as necessary. 7. Replace capillary in holder, making sure the O-ring is around the capillary before inserting it into the body. 8. Replace Cajon fitting. Note that the Cajon fitting should be replaced only hand tight. 9. Re-install the instrument cover. Appendix : Replacing Capillaries

48 A. INSPECTION AND REPLACEMENT OF CAPILLARIES Analyzer Module The following procedure should be performed on a three month basis: 1. Turn the instrument off and unplug the power cord. 2. Remove the instrument cover. 3 Locate the reaction chamber/capillary holder. [See Figure b] 4. Remove the Cajon fittings from the reaction chamber body using a 5/8" wrench. 5. Remove the glass capillaries (P/N 4121) and O-rings (P/N 4800). Inspect 0rings for cuts or abrasion. If cut or abraded, replace. [See Figure a] 6. Check the capillary for particulate deposits. Clean or replace as necessary. 7. Replace the capillary in the reaction chamber body, making sure the O-ring is around the capillary before inserting it into the body. 8. Replace the Cajon fitting. Note that the Cajon fitting should be replaced only hand tight. 9. Re-install the instrument cover. Appendix : Replacing Capillaries

49 Capillary ¼ Teflon Tube Ferrell Cajon Fitting O-ring Figure a: Exploded view of capillary and fittings in the order that they are seated in the capillary holder / reaction chamber. Reaction Chamber Sample Flow Capillary Figure b: Location of the 17C reaction chamber, where the ozone and sample flow capillaries are housed, relative to the rest of the analyzer. Figure c: Close-up view of the sample flow capillary in the reaction chamber of the 17C analyzer. Appendix : Replacing Capillaries