PINEDALE ANTICLE SPATIAL AIR QUALITY SURVEY (PASQUA) MOBILE LABORATORY MONITORING OF OZONE PRECURSORS BOULDER SOUTH ROAD SITE 10/31/ /31/2012

Transcription

1 PINEDALE ANTICLE SPATIAL AIR QUALITY SURVEY (PASQUA) MOBILE LABORATORY MONITORING OF OZONE PRECURSORS BOULDER SOUTH ROAD SITE 10/31/ /31/2012 Operational Overview Data Summaries, Data Plots and Data Review Prepared for WYOMING DEPARTMENT OF ENVIRONMENTAL QUALITY 122 West 25 th Street Cheyenne, Wyoming Prepared by Jeffrey Soltis and Robert Field University of Wyoming Atmospheric Science Department 1000 East University Avenue Laramie, WY 82071

2 TABLE OF CONTENTS 1.0 INTRODUCTION Background...7 Figure 1-1. Boulder South Road monitoring location...7 Figure 1-2. Mobile Air Quality Monitoring Laboratory location....8 Table 1-1. Geographic specifications of Boulder South Road site....9 Table 1-2. Mobile Air Quality Monitoring Laboratory monitored parameters Instrumentation and Sampling Protocols...10 Table 1-3. UW MAQML instrumentation and sampling protocols Quality Assurance DATA COLLECTION AND VALIDATION Gaseous and Meteorology Data Collection Data Validation...11 Table 2-1. Gaseous Validation Process Summary Table 2-2. Gaseous data validation flags OPERATIONAL SUMMARY Gaseous and Meteorological...12 Table 3-1. Gaseous and meteorological operational timeline GASEOUS STANDARDS SUMMARY...13 Table 4-1. UW MAQML Standards Summary Report DATA SUMMARY PRODUCTS Data Collection Summaries...14 Table 5-1. UW MAQML data collection statistics Meteorological Parameter Measurement Summaries Meteorological Data Summaries...16 Table 5-2. Boulder South Road UW MAQML meteorological data summary for the period 10/31/ /31/ Figure 5-1. Boulder South Road Wind Rose for the period 10/31/ /31/ Gaseous Pollutant Measurement Summaries Spatial Gaseous Pollutant Roses...19 Figure 5-2. Boulder South Road CH4 pollutant rose for the period 10/31/ /31/

3 Figure 5-3. Boulder South Road NMHC pollutant rose for the period 10/31/ /31/ Figure 5-4. Boulder South Road NO x pollutant rose for the period 10/31/ /31/ Figure 5-5. Boulder South Road NO pollutant rose for the period 10/31/ /31/ Figure 5-6. Boulder South Road NO 2 pollutant rose for the period 10/31/ /31/ Figure 5-7. Boulder South Road O 3 pollutant rose for the period 10/31/ /31/ Figure 5-8. Boulder South Road CO pollutant rose for the period 10/31/ /31/ Gaseous Pollutant Time Series Plots Methane...27 Table 5-3. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1-hour averages, and 24-hour averages for CH Figure 5-9. Boulder South Road CH 4 diurnal plot for the period 10/31/ /31/ Figure Boulder South Road CH 4 time series for the period 10/31/ /31/ Non-Methane Hydrocarbons...30 Table 5-4. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1-hour averages, and 24-hour averages for NMHC...31 Figure Boulder South Road NMHC diurnal plot for the period 10/31/ /31/ Figure Boulder South Road NMHC time series for the period 10/31/ /31/ Oxides of Nitrogen...33 Table 5-5. UW MAQML 5 highest daily 1-hour averages, 2nd highest daily 1-hour averages, and 24-hour averages for NO x...34 Figure Boulder South Road NO x diurnal plot for the period 10/31/ /31/ Figure Boulder South Road NO x time series for the period 10/31/ /31/ Nitric Oxide...36 Table 5-6. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1-hour averages, and 24-hour averages for NO

4 Figure Boulder South Road NO diurnal plot for the period 10/31/ /31/ Figure Boulder South Road NO time series for the period 10/31/ /31/ Nitrogen Dioxide...38 Table 5-7. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1-hour averages, and 24-hour averages for NO Figure Boulder South Road NO 2 diurnal plot for the period 10/31/ /31/ Figure Boulder South Road NO 2 time series for the period 10/31/ /31/ Ozone Data Summaries...41 Table 5-8. UW MAQML ten highest daily 1-hour average concentrations for O Table 5-9. UW MAQML summary of the ten highest daily maximum 8-hour averages. 42 Figure Boulder South Road O 3 diurnal chart for the period 10/31/ /31/ Figure Boulder South Road O 3 time series for the period 10/31/ /31/ Carbon Monoxide...44 Table UW MAQML five highest daily 1-hour averages, 2nd highest daily 1-hour averages, and 24-hour averages for CO Figure Boulder South Road CO diurnal plot for the period 10/31/ /31/ Figure Boulder South Road CO time series for the period 10/31/ /31/ CONCLUSIONS...46 APPENDIX A...48 APPENDIX B...52 APPENDIX C...61 Figure C-1. Boulder South Road CH 4 time series for the period 10/29/ /02/ Figure C-2. Boulder South Road NMHC time series for the period 10/29/ /02/ Figure C-3. Boulder South Road NO x time series for the period 10/29/ /02/ Figure C-4. Boulder South Road NO time series for the period 10/29/ /02/

5 Figure C-5. Boulder South Road NO 2 time series for the period 10/29/ /02/ Figure C-6. Boulder South Road O 3 time series for the period 10/29/ /02/ Figure C-7. Boulder South Road CO time series for the period 10/29/ /02/

6 1.0 INTRODUCTION The University of Wyoming s (UW) Atmospheric Science Department (ATSC) was contracted to operate a custom Mobile Air Quality Monitoring Laboratory (MAQML) during the period November 2011 through March Monitoring was conducted through a contract with the Pinedale Anticline Project Office (PAPO) with oversight by Wyoming Department of Environmental Quality Air Quality Division (DEQ AQD). This report describes work performed at the Boulder South Road (BSR) monitoring site during the period 10/31/ /31/2012. Other monitoring included in the monitoring design of the contract are addressed in a separate report entitled PASQUA Spatial Distribution Surveys. UW reports including the PASQUA 10/29/ /02/2011 report can be accessed online at Any comments or questions regarding this report should be addressed to: Dr. Robert Field, Principal Investigator RField1@uwyo.edu (307) University of Wyoming (UW) Atmospheric Science Department 1000 East University Avenue Laramie, WY Or Dr. Derek Montague, Principal Investigator DCM@uwyo.edu (307) University of Wyoming Atmospheric Science Department 1000 East University Avenue Laramie, WY Or Ken Rairigh, Project Manager Ken.Rairigh@wyo.gov Wyoming Department of Environmental Quality (DEQ) Air Quality Division 122 West 25 th Street Cheyenne, Wyoming

7 1.1 Background A mobile laboratory provides monitoring opportunities at locations not covered by established network sites. For the purpose of this study, the Boulder South Road location was selected as representative of an area not covered by the established DEQAQD monitoring network. This site is situated due east of the Pinedale Anticline Project Area (PAPA) and north of the Jonah Field oil and gas development. Figure 1-1 indicates the location of the BSR site relative to established oil and gas developments. Figure 1-2 shows the exact position of the MAQML monitoring location. Table 1-1 gives detailed information regarding the position and monitoring period at the BSR site. Figure 1-1. Boulder South Road monitoring location. 7

8 Figure 1-2. Mobile Air Quality Monitoring Laboratory location. 8

9 Table 1-1. Geographic specifications of Boulder South Road site. University of Wyoming Mobile Air Quality Monitoring Laboratory 10/31/ /31/2012 Boulder South Road Elevation: 7019 ft Longitude: W Latitude: N Monitoring Period: October 31, 2011 March 31, 2012 The MAQML is equipped with several gaseous pollutant analyzers as well as a meteorological monitoring station. As given in Table 1-2, the following parameters were measured: ozone (O 3 ); nitric oxide (NO), nitrogen dioxide (NO 2 ), and oxides of nitrogen (NO x ); methane (CH 4 ), and non-methane hydrocarbons (NMHC); and carbon monoxide (CO). This report presents data collected at BSR for the period 31 October 2011 through 31 March Ambient concentrations of O 3, NO, NO 2, and NO x, CH 4, NMHC, and CO are continuously monitored according to EPA approved methods. Wind speed, wind direction, temperature, barometric pressure and relative humidity are monitored to understand local meteorological conditions. Project performance goals includes adherence to EPA monitoring guidelines. Details of the monitoring design and quality assurance program are given in the Quality Assurance Project Plan (QAPP) for the Pinedale Anticline Spatial Air Quality Assessment (PASQUA) (Rev 2.0, October 2011). Table 1-2. Mobile Air Quality Monitoring Laboratory monitored parameters. Gaseous Parameters Ozone (O 3 ) Nitric Oxide (NO) Nitrogen Dioxide (NO 2 ) Oxides of Nitrogen (NO x ) Methane (CH 4 ) Non-Methane Hydrocarbons (NMHC) Carbon Monoxide (CO) University of Wyoming Mobile Air Quality Monitoring Laboratory 10/31/ /31/2012 Meteorological Parameters Wind Speed (WS) Wind Direction (WD) Barometric Pressure Temperature Relative Humidity (RH) 9

10 1.2 Instrumentation and Sampling Protocols Table 1-3 shows key characteristics of monitoring instrumentation in the MAQML. Measurement frequencies of 1-minute and 5-minute were used for gaseous parameters. A sampling rate of 1-minute was used for the Thermo-Fisher 55i and Thermo-Fisher 48i instruments to maximize the number of samples. For the former, this was due to the importance of this parameter. For the latter, this was to ensure that blank span corrections did not result in excessive loss of ambient measurements. Table 1-3. UW MAQML instrumentation and sampling protocols. University of Wyoming Mobile Air Quality Monitoring Laboratory 10/31/ /31/2012 Component Instrumentation Height Frequency Parameter Gaseous Thermo-Fisher 49i 5 meters 5 minute O 3 Thermo-Fisher 42i 5 meters 5 minute NO, NO 2, NO x Thermo-Fisher 48i 5 meters 1 minute CO Thermo-Fisher 55i 5 meters 1 minute CH 4, NMHC Meteorology Vaisala Weather Transmitter WXT510 5 meters 1 minute Wind Speed Wind Direction Temperature Pressure Relative Humidity 1.3 Quality Assurance Quality assurance procedures are provided in the PASQUA QAPP. Of particular importance is the initial set-up of the MAQML, site operating protocols and post processing procedures. Proper site operation includes calibration, instrument maintenance, and troubleshooting. Independent auditing of ozone, oxides of nitrogen, total hydrocarbons, and trace level carbon monoxide instrumentation was conducted by T&B Systems, an independent contractor for DEQ-AQD. As noted in the relevant document (see Appendix B), audits reveal no issues and excellent performance for all instrumentation. There were no occasions with non-compliant performance. UW conducted internal audits of all instrumentation on a monthly basis, including at the end of the monitoring period. Internal audit results are referenced for final data validation procedures. Routine operation and data collection activities are systematic and follow procedures as detailed in instrument-specific Standard Operating Procedures (SOP). 10

11 2.0 DATA COLLECTION AND VALIDATION 2.1 Gaseous and Meteorology Data Collection Raw data are uploaded daily via cellular modem to the ATSC FTP server. Data is also collected during site visits. Inorganic pollutant data are available via the project website to review operational status and measurement parameters. The purpose of daily uploads is to perform data quality checks and to concatenate current data to previously collected data Data Validation This project employs a three-level data validation process. These levels, and the validation codes that designate them, are defined in Tables 2-1 and 2-2, respectively. Table 2-1. Gaseous Validation Process Summary. Level 0 Validation Level 0 data are obtained directly from the data loggers that acquire the data in the field. Averaging times represent the minimum intervals recorded by the data logger, which do not necessarily correspond to the averaging periods specified for the database files. Level 0 data have not been edited for instrument downtime, nor have procedural adjustments for baseline and span changes been applied. Level 0 data are consulted on a regular basis to ascertain instrument functionality and to identify potential episodes prior to receipt of Level 1 data. Level 1 Validation Level 1 data have passed several validation tests applied by the measurement investigator prior to data submission. The general features of Level 1 are: 1) removal of values when monitoring instruments fail specified validation criteria; 2) flagging measurements when significant deviations from measurement assumptions have occurred; 3) verifying computer file entries against data sheets, where appropriate; 4) replacement of data from a backup data acquisition system in the event of failure of the primary system; and 5) adjustment of measurement values for quantifiable baseline and span or interference biases. Level 2 Validation Level 2 These data have been assembled into a collated data file. Level 2 validation is the first step in data analysis. Level 2 validation involves the testing of measurement assumptions, comparison of collocated instruments, and internal consistency tests. 11

12 Table 2-2. Gaseous data validation flags. Code A S Z M Mx Meaning Valid ambient data Span cylinder check data and calibration curve span cylinder data External audit data Basic invalid data that includes instrument warm-up data and transition of span to ambient data Malfunction data that has a secondary code that relates to a specific indentified reason as noted below: MA Malfunction air supply MP Malfunction power supply MH Malfunction hydrogen supply MD Malfunction data acquisition system 3.0 OPERATIONAL SUMMARY 3.1 Gaseous and Meteorological Table 3-1. Gaseous and meteorological operational timeline. Date October 31, 2011 November 17, 2011 November 18, 2011 December 14, 2011 January 18, 2012 January 19, 2012 January 31, 2012 February 22, 2012 March 21, 2012 March 28, 2012 April University of Wyoming Pinedale Anticline Spatial Air Quality Assessment Operational Summary 10/31/ /31/2012 Summary Lab startup. MAQML inorganic instrument calibration (internal audit). Site visit. MAQML inorganic instrument calibration (internal audit). Site visit. MAQML inorganic instrument calibration (internal audit). Site visit. MAQML inorganic instrument calibration (internal audit). Site visit. MAQML 42i NO X instrument calibration. hydrogen generator maintenance. Thermo 55i column burn (internal audit). Zero air generator failure. RMA to Thermo. T&B Systems quality assurance audit. Site visit. MAQML inorganic instrument calibration (internal audit). Install repaired zero air generator. Site visit. MAQML inorganic instrument calibration (internal audit). Lab shutdown. 12

13 4.0 GASEOUS STANDARDS SUMMARY Ambient concentrations of O 3 and NO 2 are regulated by DEQ-AQD and EPA under Wyoming Ambient Air Quality Standards (WAAQS) and EPA National Ambient Air Quality Standards (NAAQS) provisions of the Clean Air Act. Values measured by PASQUA are presented with corresponding NAAQS/WAAQS in Table 4-1. This table is intended for comparative purposes as the PASQUA study was conducted over a period of five months. This comparison is for context and does not have direct applicability to NAAQS or WAAQS. The NAAQS standard for O 3 was updated by EPA in March 2008, and is regulated at ppm over an 8-hour period. An exceedance of the NAAQS standard occurs when an 8-hour average O3 concentration is greater than or equal to ppm (75 ppb). A violation of the standard occurs when the three-year average of the fourth highest daily maximum 8-hour average ozone concentration exceeds ppm. NAAQS for NO2 is an annual arithmetic mean of the one-hour NO2 values, 53 ppb. There is an additional 1-hour NAAQS for NO2 effective on April 12 th The limit value for NO2 of 100 ppb is based on the eighth highest (98 %tile) of the annual distribution of the maximum daily 1-hour values. Although a comparison value cannot be calculated for NO 2, Table 4-1 shows that ozone levels did not exceed the NAAQS standard value for the rolling 8-hour average. Table 4-1. UW MAQML Standards Summary Report. Parameter University of Wyoming Mobile Air Quality Monitoring Laboratory 10/31/ /31/2012 NAAQS Measured Averaging Standard Measured Value Dates Time Ozone* Rolling 8-hour ppm Highest Daily Max: 4th Highest Daily Max: Nitrogen Dioxide Annual 53 ppb Arithmetic Mean /09/ /10/ hour 100 ppb 98 %tile 21 12/16/2011 n/a n/a * See Appendix A, EPA Memo titled "Implementation of Ozone National Ambient Air Quality Standard" dated 22 September

14 5.0 DATA SUMMARY PRODUCTS The following sections present summary information for PASQUA monitoring performed during the period 31 October 2011 through 31 March These sections assess data recovery and each of the parameters considered in PASQUA. Section 5.1 considers data recovery for all measured parameters. Section 5.2 considers meteorological parameters with particular attention given to wind speed and wind direction. Section 5.3 considers values for gaseous pollutant measurements. These sections illustrate behavior through pollutant roses, temporal, and diurnal plots. 5.1 Data Collection Summaries Data recovery information presented in Table 5-1 is calculated from hourly averaged data. For Table 5-1 the total number of possible data points, in relation to the total number of valid ambient data points, are shown. The number possible is the period from when data is produced from the instrument, i.e. from switch on until switch off. Collected data exclude equipment warm-up, power outages, instrument malfunction, and/or repair servicing. The percent collected value is equal to number collected divided by the number possible. Valid data are ambient data that exclude calibration, span/zero, audit values, canister analysis, system testing and validation screening values. Table 2-2 lists the codes and associated cause of invalidation. Greater detail is given in the QAPP. Completeness criteria are indicated by the calculation of the percentage of valid data. This value is the number of valid ambient data points divided by the number possible. Completeness criteria were exceeded for all measurement parameters. 14

15 Table 5-1. UW MAQML data collection statistics. University of Wyoming Mobile Air Quality Monitoring Laboratory Data Collection Statistics Final Validation 10/31/ /31/2012 Data Recovery Valid Data Parameter Interval Par Code No. Possible No. Collected % Collected No. Valid % Valid Ozone Hourly Average O % % Nitric Oxide Hourly Average NO % % Oxides of Nitrogen Hourly Average NO X % % Nitrogen Dioxide Hourly Average NO % % Carbon Monoxide Hourly Average CO % % Methane Hourly Average CH % % Non-Methane Hydrocarbons Hourly Average NMHC % % Wind Direction Hourly Average WD % % Wind Speed Hourly Average WS % % Temperature Hourly Average TEMP % % Relative Humidity Hourly Average RH % % Pressure Hourly Average PRES % % Performance Goals: Completeness Criteria Listing from QAAP O 3 NO NO x NO 2 CO CH 4 NMHC Wind Speed Wind Direction 75% 75% 75% 75% 80% 80% Number possible is equal to the total number of hours running time. Number collected is equal to the total number of hours running time after subtracting power outages and instrument malfunction or repair servicing. Number valid is equal to number collected after removing calibration, span/zero, audit values, canister analysis, system testing and validation screening values. 15

16 5.2 Meteorological Parameter Measurement Summaries Continuous air temperature, barometric pressure, wind speed and wind direction values are measured using a Vaisala WXT510 Weather Transmitter. Summaries of air temperature, barometric pressure, wind speed and wind direction measurements at the MAQML are presented in this section Meteorological Data Summaries Table 5-2 shows the meteorological data summary for the MAQML at the BSR monitoring site. Data collection commenced at the on 31 October and concluded 31 March The site is located on open ground without significant influence from proximate structures. Wind speed and direction data for this site are displayed as a wind rose presented in Figure 5-1. This site was selected to be representative of different downwind or upwind situations relative to the PAPA and Jonah developments. Table 5-2. Boulder South Road UW MAQML meteorological data summary for the period 10/31/ /31/2012. University of Wyoming Mobile Air Quality Monitoring Laboratory Meteorological Data Summary Final Validation 10/31/ /31/2012 Parameter Value Units Number Standard Deviation WIND SPEED Average 2.9 m/s Maximum 14.1 TEMPERATURE Average -3.3 C Maximum 19.3 Minimum RELATIVE HUMIDITY Average 69.2 % Maximum 94.6 Minimum 15.1 PRESSURE Average MBAR Maximum 800 Minimum

17 The BSR site was located on open ground proximate to US Highway 191 (Figure 1-2). Figure 5-1 shows three distinct areas of influence. The first, from the northwest, is associated with a greater proportion of relatively high wind speeds of between 7 and 13 m/s. The second, from the south, is associated with a greater proportion of relatively low wind speeds below 4 m/s. The third, from the southeast, is associated with a comparatively greater proportion of wind speeds between 4 and 7 m/s. There were relatively few occasions with wind directions from the northeast quadrant. This direction would be associated with the Wind River Range. The northwest direction is associated with airflow from the Gros Ventre and northern Wyoming Range. South flows are associated with airflow from the southern Green River Basin area. This is anticipated given the position of BSR monitoring site. During this monitoring period Figure 5-1 shows that BSR may be considered frequently downwind of the PAPA but predominantly downwind of both the Jonah Field development and the PAPA. During periods of light winds, direction may be highly variable, but appear to come primarily from the south. As indicated by Table 5-2, meteorological conditions are typical for the fivemonth monitoring period that encompassed the winter months. Average wind speed, pressure and relative humidity are typical for this area. The average temperature of -3.3 C is warmer than the value of -3.7 C in the previous PASQUA monitoring period. The minimum value of C is warmer than the corresponding value of C. The maximum value of 19.3 C is warmer than the corresponding value of 16.5 C. 17

18 Figure 5-1. Boulder South Road Wind Rose for the period 10/31/ /31/2012. Wind Rose m/s 10/31/ /31/

19 5.3 Gaseous Pollutant Measurement Summaries Continuous CH 4 and NMHC values were measured using Thermo-Fisher 55i Direct Methane, Non-Methane Hydrocarbon Analyzer. Summaries of CH 4 and NMHC measurements are presented in sections and Continuous NO x, NO 2 and NO values are measured using a Thermo-Fisher 42i Chemiluminescent NO x -NO 2 -NO Analyzer. Summaries of NO x, NO 2 and NO measurements are presented in sections , and , respectively. NO 2 is a regulated pollutant with an annual and a 1-hour standard. Continuous O 3 values are measured using a Thermo-Fisher 49i UV Photometric O 3 Analyzer. A summary of ozone measurements is presented in section Ozone is a regulated air pollutant with a rolling 8-hour standard. Continuous CO values were measured using Thermo-Fisher 48i Analyzer. Summaries of CO measurements are presented in section Summaries of gaseous pollutant measurements are given for the MAQML. Section explores pollutant roses. Pollutant measurements are displayed temporally in section by pollutant. Reference is made to previous PASQUA monitoring time series figures that are given in Appendix C Spatial Gaseous Pollutant Roses In light of anticipated benefits of the site location, a brief overview of pollution roses provides context for considering the temporal behavior shown by diurnal and longer-term temporal data plots in the subsequent sub-sections. Pollution roses given in Figure 5-2 for CH 4 shows that Northwesterly winds had the greatest proportion of lowest concentrations and the lowest proportion of high concentrations. The reverse behavior was evident for Southerly winds with relatively infrequent lower concentration and greater proportions of higher concentration levels. Similar behavior was evident for NMHC (Figure 5-3), oxides of nitrogen (Figure 5-4), nitric oxide (Figure 5-5), nitrogen dioxide (Figure 5-6), ozone (Figure 5-7), and carbon monoxide (Figure 5-8). The similarity of behavior indicates that while these compounds are likely emitted from different emission sources, these sources are distributed within the air-flow regime measured by the MAQML, and as such are affected equally by meteorological conditions. Ozone exhibited a different pattern with a relatively even distribution of midand higher levels while the greatest proportion of lower concentrations were associated with Southerly wind directions. This behavior is due to the secondary nature of ozone formation with highest levels associated with daylight hours. 19

20 Figure 5-2. Boulder South Road CH4 pollutant rose for the period 10/31/ /31/2012. Pollutant Rose CH 4 Quantiles ppm 10/31/ /31/

21 Figure 5-3. Boulder South Road NMHC pollutant rose for the period 10/31/ /31/2012. Pollutant Rose NMHC Quantiles ppm 10/31/ /31/

22 Figure 5-4. Boulder South Road NO x pollutant rose for the period 10/31/ /31/2012. Pollutant Rose Oxides of Nitrogen Quantiles ppb 10/31/ /31/

23 Figure 5-5. Boulder South Road NO pollutant rose for the period 10/31/ /31/2012. Pollutant Rose Nitric Oxide ppb 10/31/ /31/

24 Figure 5-6. Boulder South Road NO 2 pollutant rose for the period 10/31/ /31/2012. Pollutant Rose Nitrogen Dioxide ppb 10/31/ /31/

25 Figure 5-7. Boulder South Road O 3 pollutant rose for the period 10/31/ /31/2012. Pollutant Rose Ozone Quantiles ppb 10/31/ /31/

26 Figure 5-8. Boulder South Road CO pollutant rose for the period 10/31/ /31/2012. Pollutant Rose Carbon Monoxide Quantiles ppb 10/31/ /31/

27 5.3.2 Gaseous Pollutant Time Series Plots The following subsections describe data generated for each pollutant. Data are displayed in table form and graphically. Diurnal plots, influenced by changing dispersion conditions throughout the day, are useful for gaining an insight into the contributions of various emission sources upon meteorologically driven variation. This section includes diurnal behavior plots constructed from hourly averaged values, an approach that enables hourly variations to be visualized. Longer time series plots that display sequential data are more useful to illustrate trends and deviations from normal conditions during the given monitoring period. Reference is made to previous PASQUA monitoring time series figures that are given in Appendix C Methane As indicated by the pollution rose diagrams for CH 4, elevated concentrations were most associated with southerly wind directions. Table 5-3 presents highest and second highest daily 1-hour average CH 4 concentrations and highest daily twenty-four hour averages. Table 5-3 shows that highest elevated hourly averages were present during November, December and February. Dispersion conditions are generally poorest during colder conditions and consequently ambient concentrations tend to be elevated. Although high values are indicated for all winter months, as shown by Table 5-3, the highest values are at least 1 ppm lower than previous years' observations. Highest levels generally occur during early morning hours when the atmosphere is most stable. One instance of elevated levels does occur at 22:00 on 05 November Figure 5-9 shows the diurnal plot and Figure 5-10 shows the time series plot of ambient CH 4 concentrations for the entire operational period. The most noticeable feature of the diurnal plot is that the highest levels occur during early morning hours, followed by somewhat flat levels throughout the rest of the day. Previous measurements have shown much higher levels during the midnight to 03:00 time period. The time series plot for CH 4 expands the diurnal behavior and displays long-term trends and intermittent episodes unrelated to diurnal patterns. Figure 5-9 shows that levels of methane are frequently above background with a contribution from local emission sources. The role of meteorology is important with elevated concentrations most evident during late November and early March. The lack of any period of extended elevated levels is striking, in particular, the relatively low levels occurring during the month of January when winter drilling typically provides an emission spike. 27

28 Table 5-3. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1- hour averages, and 24-hour averages for CH 4. University of Wyoming Mobile Air Quality Monitoring Laboratory 5 Highest Daily 1-Hour Averages, 2nd Highest Daily 1-Hour Averages, and 24-Hour Averages for CH 4 Final Validation 10/31/ /31/2012 Highest Daily 1-Hour Averages Value Date Hour Concentration ppm 1 11/21/11 09: /05/11 05: /09/11 06: /18/11 07: /07/12 09: nd Highest Daily 1-Hour Averages 1 11/21/11 08: /05/11 22: /03/12 08: /02/12 01: /04/11 05: Highest Daily 24-Hour Averages 1 11/21/ : /07/ : /18/ : /23/ : /03/ :

29 Figure 5-9. Boulder South Road CH 4 diurnal plot for the period 10/31/ /31/ CH4, ppm Hour Hourly Maximum Hourly Average Hourly Minimum Figure Boulder South Road CH 4 time series for the period 10/31/ /31/

30 Non-Methane Hydrocarbons Table 5-4 presents highest and second-highest daily one-hour average NMHC concentrations and highest daily twenty-four hour averages. Highest hourly NMHC concentrations occur concurrently with approximately fifty percent of the highest hourly CH 4 levels. Two of the five highest twenty-four hour averages are common, most likely natural gas production activities. The three divergences are an indication of an NMHC source that is not directly associated with CH 4, for example water treatment activity at the Anticline Disposal Facility With respect to the diurnal plots, the most interesting observation is the presence of relatively steady levels throughout the day-time period. This contrasts with previous observations, which showed an increase in levels in the afternoon. The time series plot for NMHC expands the diurnal behavior and allows for visualization of longer-term trends and intermittent episodes unrelated to diurnal patterns. With respect to the time series plots, highest levels occur during November, before the onset of winter drilling stipulations. Elevated levels during December are not associated with particularly high levels CH 4. The January period displays relatively low levels of NMHCs, with a gradual rise, and several periods of elevated levels during February. The behavior of the time series figure for NMHC appears similar in terms of spikes related to measurement of emissions but different in terms of the levels reached, with much lower reported concentrations in the winter of This reflects the CH 4 trend shown in the previous section. 30

31 Table 5-4. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1- hour averages, and 24-hour averages for NMHC. University of Wyoming Mobile Air Quality Monitoring Laboratory 5 Highest Daily 1-Hour Averages, 2nd Highest Daily 1-Hour Averages, and 24-Hour Averages for NMHC Final Validation 10/31/ /31/2012 Highest Daily 1-Hour Averages Value Date Hour Concentration ppm 1 11/21/11 09: /18/11 07: /08/12 15: /05/11 05: /20/11 21: nd Highest Daily 1-Hour Averages 1 02/08/12 19: /21/12 12: /21/11 08: /09/11 06: /07/12 09: Highest Daily 24-Hour Averages 1 11/21/ : /08/ : /18/ : /24/ : /11/ :

32 Figure Boulder South Road NMHC diurnal plot for the period 10/31/ /31/ NMHC, ppm Hour Hourly Maximum Hourly Average Hourly Minimum Figure Boulder South Road NMHC time series for the period 10/31/ /31/

33 Oxides of Nitrogen NO x measurements, as a sum of NO and NO 2, are a hybrid primary and secondary pollutant. NO is considered a primary pollutant of combustion systems; NO 2 is classified as a secondary pollutant. While some combustion systems can directly produce NO 2, more often this pollutant is formed from the reaction of NO to form NO 2. This reaction may occur during the emission process or at a position downwind. Measured NO x concentrations can indicate the influence of both emission sources and reaction chemistry, therefore the position of sampling relative to emission sources is an important consideration. Ignoring the influence of seasonal variation upon emissions and atmospheric chemistry, locations close to direct emission sources will tend to have relatively high NO compared to those at sites downwind of emission sources. Table 5-5 presents highest and second highest daily one-hour average NO x concentrations, and highest daily twenty-four hour averages. Times represented in this table are generally different than those given for the hydrocarbon measurements. Since the measurements are simultaneous, this behavior could be due to a different balance of contributing emission sources for NO x than for methane and NMHC. The five highest and second highest one-hour values occur during times associated with vehicle traffic. When considering the highest daily average values, the importance of seasonality is shown with highest measurements during colder months. With respect to the diurnal plots, Figure 5-13, the typical behavior is a morning peak followed by a mid day trough and an early evening peak. While there is some similarity with respect to night-time high and mid-afternoon low, hours associated with traffic flow have the highest concentrations. The NO x concentration during morning peak hours is generally higher than the afternoon peak. The time series plot shown in Figure 5-14 shows high concentrations during all months, with generally low levels during January

34 Table 5-5. UW MAQML 5 highest daily 1-hour averages, 2nd highest daily 1-hour averages, and 24-hour averages for NO x. University of Wyoming Mobile Air Quality Monitoring Laboratory 5 Highest Daily 1-Hour Averages, 2nd Highest Daily 1-Hour Averages, and 24-Hour Averages for NO x Final Validation 10/31/ /31/2012 Highest Daily 1-Hour Averages Value Date Hour Concentration ppb 1 12/20/11 06: /09/11 06: /12/11 06: /01/12 07: /14/12 06: nd Highest Daily 1-Hour Averages 1 01/03/12 06: /10/12 07: /19/11 18: /06/11 06: /06/12 08: Highest Daily 24-Hour Averages 1 02/02/ : /03/ : /06/ : /19/ : /07/ :

35 Figure Boulder South Road NO x diurnal plot for the period 10/31/ /31/ NOx, ppb Hour Hourly Maximum Hourly Average Hourly Minimum Figure Boulder South Road NO x time series for the period 10/31/ /31/

36 Nitric Oxide Table 5-6 presents highest and second highest daily one hour average NO concentrations, and highest daily twenty-four hour averages. The times that are represented in this table are very similar to those given in Table 5-5, in particular for onehour maximum values. This similarity is illustrated by the behaviors shown in Figures 5-15 and The diurnal plot shows a rise from 05:00 to a peak at 06:00 with a decline until 15:00. Apart from some isolated maxima values an afternoon peak is absent. The time series plot of ambient NO concentrations also shows a greater consistency and less seasonality for NO values over the operational period. Table 5-6. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1- hour averages, and 24-hour averages for NO. University of Wyoming Mobile Air Quality Monitoring Laboratory 5 Highest Daily 1-Hour Averages, 2nd Highest Daily 1-Hour Averages, and 24-Hour Averages for NO Final Validation 10/31/ /31/2012 Highest Daily 1-Hour Averages Value Date Hour Concentration ppb 1 12/20/11 06: /03/12 06: /10/12 07: /09/11 06: /12/11 06: nd Highest Daily 1-Hour Averages 1 12/06/11 06: /19/11 06: /01/12 07: /06/12 08: /04/11 05: Highest Daily 24-Hour Averages 1 12/06/ : /20/ : /19/ : /14/ : /03/ :

37 Figure Boulder South Road NO diurnal plot for the period 10/31/ /31/ NO, ppb Hour Hourly Maximum Hourly Average Hourly Minimum Figure Boulder South Road NO time series for the period 10/31/ /31/

38 Nitrogen Dioxide Table 5-7 presents highest and second highest daily one-hour average NO 2 concentrations, and highest daily twenty-four hour averages. Besides the highest twentyfour hour values, times represented in this table show higher NO 2 one-hour values at different times to those of NO. This is be expected given NO 2 is a secondary pollutant. Figures 5-17 and 5-18 represent the diurnal and time series plots of ambient NO 2 concentrations during operational period. With respect to the diurnal plot for NO 2, the typical behavior is a morning peak followed by a mid day trough and a greater late afternoon peak in concentration. The afternoon pattern shows divergence from that shown for NO x and NO. This can be expected for a secondary pollutant whose main production route is through daytime photochemical reaction. NO 2 is a product from the reaction: NO + O 3 NO 2 + O 2. This reaction consumes O 3 whereby NO 2 is produced via photochemical production during which it may serve as an ozone precursor, as shown below: NO 2 + sunlight NO + O, then O + O 2 O 3 When peroxy and hydro-peroxy radical chemistry is considered, there is net production of NO 2 which does not consume O 3. During this time NO 2 may also serve as a precursor to O 3 based on this reaction. The time series plots of NO 2 indicate a similar behavior as that of NO x, albeit with a lower magnitude with the afternoon peak relatively elevated. 38

39 Table 5-7. UW MAQML five highest daily 1-hour averages, 2nd highest daily 1- hour averages, and 24-hour averages for NO 2. University of Wyoming Mobile Air Quality Monitoring Laboratory 5 Highest Daily 1-Hour Averages, 2nd Highest Daily 1-Hour Averages, and 24-Hour Averages for NO 2 Final Validation 10/31/ /31/2012 Highest Daily 1-Hour Averages Value Date Hour Concentration ppb 1 12/09/11 06: /19/11 18: /14/12 06: /12/11 06: /01/12 07: nd Highest Daily 1-Hour Averages 1 01/31/12 06: /16/11 07: /20/11 06: /07/12 06: /21/11 17: Highest Daily 24-Hour Averages 1 02/02/ : /03/ : /06/ : /19/ : /07/ :

40 Figure Boulder South Road NO 2 diurnal plot for the period 10/31/ /31/ NO2, ppb Hour Hourly Maximum Hourly Average Hourly Minimum Figure Boulder South Road NO 2 time series for the period 10/31/ /31/

41 Ozone Data Summaries Table 5-8 presents the ten highest daily one-hour average O 3 concentrations that occurred. Two episodic groupings of elevated one hour ozone occur: February 07-08, 2012, and March 08-11, Two episodic groupings of elevated eight hour ozone occur: March 08-11, 2012, and March 24-29, There were no dates during which concentrations were above the NAAQS standard value of ppm. If the UW site was used for regulatory purposes the fourth highest daily 8-hr average value would be 60.3 ppb. Figures 5-19 through 5-20 represent the diurnal plot and time series plot of ambient O 3 concentrations for the operational period. With respect to the diurnal plot the typical behavior is a rise from an early morning trough to an afternoon peak followed by a decline. Figure 5-20 shows the significance of ozone season with all elevated values during the period late January through March. 41

42 Table 5-8. UW MAQML ten highest daily 1-hour average concentrations for O 3. University of Wyoming Mobile Air Quality Monitoring Laboratory 10 Highest Daily 1-Hour Average Maximum Concentrations 10/31/ /31/2012 Value Date Hour Concentration ppb 1 03/09/12 12: /21/12 12: /08/12 15: /08/12 15: /15/12 16: /02/12 18: /10/12 17: /07/12 16: /24/12 13: /11/12 11:00 64 Table 5-9. UW MAQML summary of the ten highest daily maximum 8-hour averages. University of Wyoming Mobile Air Quality Monitoring Laboratory Summary of the 10 Highest Daily Maximum 8-Hour Averages 10/31/ /31/2012 Value Date Hour Concentration ppb 1 03/09/12 18: /08/12 19: /08/12 18: /10/12 18: /11/12 17: /02/12 19: /29/12 16: /26/12 19: /27/12 17: /24/12 17:

43 Figure Boulder South Road O 3 diurnal chart for the period 10/31/ /31/ Ozone, ppb Hour Hourly Maximum Hourly Average Hourly Minimum Figure Boulder South Road O 3 time series for the period 10/31/ /31/

44 Carbon Monoxide Table 5-10 presents highest and second highest daily 1-hour average CO concentrations, and highest daily twenty-four hour averages that occurred. Levels show the dominance of tropospheric background throughout the monitoring period. While some variation is apparent this appears to be associated with poor dispersion during colder months. Table UW MAQML five highest daily 1-hour averages, 2nd highest daily 1- hour averages, and 24-hour averages for CO. University of Wyoming Mobile Air Quality Monitoring Laboratory 5 Highest Daily 1-Hour Averages, 2nd Highest Daily 1-Hour Averages, and 24-Hour Averages for CO Final Validation 10/31/ /31/2012 Highest Daily 1-Hour Averages Value Date Hour Concentration ppb 1 12/11/11 16: /19/11 19: /24/11 15: /28/11 09: /11/11 12: nd Highest Daily 1-Hour Averages 1 12/19/11 18: /28/11 08: /18/11 16: /11/11 13: /05/12 14: Highest Daily 24-Hour Averages 1 12/19/ : /11/ : /28/ : /03/ : /02/ :

45 Figure Boulder South Road CO diurnal plot for the period 10/31/ /31/ CO. ppb Hour Hourly Maximum Hourly Average Hourly Minimum Figure Boulder South Road CO time series for the period 10/31/ /31/

46 6.0 CONCLUSIONS For the five-month duration of the study, the following conclusions may be drawn from the basic summary data: The mobile laboratory operated and obtained data that were above the required data capture criteria for all 12 measured parameters (gaseous pollutants and meteorological parameters). Wind rose diagrams indicated two main wind fields of importance to the normal conditions in study area a northwesterly Gros Ventre pattern and a southerly wind pattern. Northeasterly wind directions were rare. Compared to the winter of 2011 night-time low and daytime high temperatures were elevated. For the duration of monitoring, the MAQML site location was often downwind of either the Jonah development or the PAPA development. Pollution rose diagrams indicate wind flows from the south had the highest pollution levels for most of the measurements. Elevated ozone levels are evident from most wind directions, including southerly and northwesterly flows. Time series plots reveal the role of meteorology. The coldest season is associated with higher pollution levels, most likely due to the influence of temperature inversions upon atmospheric stability and thereby mixing behavior. Methane (CH 4 ) levels while showing frequent, almost continual, elevations above tropospheric background differ from those during the winter of In 2012 episodic peaks of CH 4 are less frequent and also are less pronounced. The levels of NMHC reflect the behavior of CH 4 with much lower values reported in 2012 compared to The diurnal curve of NO x, NO and NO 2 shows well defined peak periods that are comparable to 2012, however afternoon minimum values appear lower in The measured levels of NO x, NO and NO 2 are lower in 2011 compared to 2012, however this difference is less marked than for CH 4 and NMHC. Episodic ozone behavior was evident during the time period from early February through March. Episodic ozone levels were markedly less frequent in occurrence and magnitude during 2012 compared to While monitoring was only performed for 5 months, the ozone NAAQS level was not exceeded during the monitoring period at the MAMQL. The ambient concentration of CO reflected the dominance of tropospheric background (approximately 100 to 200 ppb) with reported values similar to those in Lower concentrations of pollution are reported for most pollutants in particular ozone, and NMHC for 2011 compared to Daily and hourly maximum data shows the difference between primary and secondary air pollutants. Primary pollutant peaks most often occurred during the period November through January, while ozone peaks predominately occurred in March. 46

47 The peak values for CH 4, NMHC and NOx indicate both the commonality and divergence of contributing emission sources, as their behavior patterns both match and differ during the monitoring period. 47

48 APPENDIX A EPA NAAQS MEMO 48

49 49

50 50

51 51

52 APPENDIX B T & B AUDIT 52

53 FIRST QUARTER 2012 QUALITY ASSURANCE AUDIT REPORT for the WYOMING DEPARTMENT OF ENVIRONMENTAL QUALITY AIR MONITORING NETWORK Prepared for Wyoming Department of Environmental Quality Air Quality Division Herschler Building 122 W. 25 th St. Cheyenne, WY FEBRUARY 2012 Prepared by TECHNICAL & BUSINESS SYSTEMS, INC AVENUE HALL, UNIT 9 VALENCIA, CA (661)

54 5.13 UNIVERSITY OF WYOMING (BOULDER SOUTH ROAD) Site Location!"#$%&'#$&%$()*+'#,$+'$--.$/01$-2345$6)7'"$8+'&'9,#$+:,$4;<.$4=>$4<345$?#%'$ Longitude (GPS) Station Equipment Summary, Audit Results and Recommendations Table 1. Site Monitoring Equipment Site: UW Mobile Lab Date: 01/31/12 AMBIENT AIR QUALITY MONITORS Parameter Manufacturer Model Serial No. Range Last Cal Ozone Thermo 49i CM ppm NA Nitric Oxide Thermo 42i ppm NA Nitrogen Oxides Thermo 42i ppm NA Nitrogen Dioxide Thermo 42i ppm NA Carbon Monoxide (Trace Level) Thermo 48i-TLE NA 1 ppm NA Total Hydrocarbons Thermo 55i ppm NA Table Monitoring equipment at UW Mobile Lab. Site: UW Mobile Lab (Boulder-South) Project: University of Wyoming Operator: University of Wyoming AMBIENT AIR QUALITY MONITORS Audit Max Diff. DAS DAS DAS Date Parameter (%) Slope Intercept Correlation 1/31/2012 Ozone /31/2012 Total Hydrocarbons /31/2012 Nitric Oxide /31/2012 Nitrogen Oxides /31/2012 Nitrogen Dioxide /31/2012 Carbon Monoxide (TL) Audit Criteria: Max Diff ±15%, Slope ± 0.15: Intercept 0 ± ppm (THC 0 ± 0.9 ppm); Correlation > ; Trace Level (Audit levels 1-3): Max Diff ±15% Slope ± 0.15 OR ±0.03 ppm for CO (Whichever is greater) Table Audit results for UW Mobile Lab. Key Audit Findings No problems were noted Performance Audit Reports The performance audit reports for the air quality instrumentation follow

55 AUDIT RECORD Avenue Hall Unit 9 NITRIC OXIDE Valencia, CA (661) Date: 01/31/12 Site Name: UW Mobile Lab (Boulder-South) Start: 13:20 MST Operator: University of Wyoming Finish: 17:00 MST Project: University of Wyoming Audited by: David Yoho Witness: Brittni Emery Analyzer make: Thermo Model: 42i Serial No.: Filter: NA Sample flow: lpm Span setting: Zero setting: Vacuum: N/A Range: PPM Mode: N/A Last cal.: NA NO PPM PPM PPM Audit Input DAS Dif Point (X) (Y) (%) NA Linear Regression: (Y=PPM Corrected, X=PPM Input) DAS Slope: Intercept: Correlation: Comments: No problems noted. Certification Audit Equipment Make Model ID Date Dilution System: API M700EU 83 1/24/12 Zero Air System: API NA Calibration Gas: SMI Multi JJ /17/

56 AUDIT RECORD Avenue Hall Unit 9 OXIDES OF NITROGEN Valencia, CA (661) Date: 01/31/12 Start: 13:20 MST Finish: 17:00 MST Audited by: David Yoho Witness: Brittni Emery Site Name: UW Mobile Lab (Boulder-South) Organization: University of Wyoming Project: University of Wyoming Analyzer make: Thermo Model: 42i Serial No.: Filter: NA Sample flow: N/A Span setting: Zero setting: Vacuum: N/A Range: PPM Last cal.: NA NOx PPM PPM PPM Audit Input DAS Dif Point (X) (Y) (%) NA Linear Regression: (Y=PPM Corrected, X=PPM Input) DAS Slope: Intercept: Correlation: Comments: No problems noted. Certification Audit Equipment Make Model ID Date Dilution System: API M700EU 83 1/24/12 Zero Air System: API NA Calibration Gas: SMI Multi JJ /17/

57 AUDIT RECORD Avenue Hall Unit 9 NITROGEN DIOXIDE Valencia, CA (661) Date: 01/31/12 Start: 13:20 MST Finish: 17:00 MST Audited by: David Yoho Witness: Brittni Emery Site Name: UW Mobile Lab (Boulder-South) Organization: University of Wyoming Project: University of Wyoming Analyzer make: Thermo Model: 42i Serial No.: Converter T.: 327 deg C Ozone flow: NA Last cal.: NA Range: PPM NO2 PPM PPM PPM Audit Input DAS Dif Point (X) (Y) (%) NA Linear Regression: (Y=PPM Corrected, X=PPM Input) DAS Slope: Converter Intercept: Efficiency Correlation: % Comments: No problems were noted. Certification Audit Equipment Make Model ID Date Dilution System: API M700EU 83 1/24/12 Zero Air System: API NA Calibration Gas: SMI Multi JJ /17/

58 AUDIT RECORD Avenue Hall Unit 9 TOTAL HYDROCARBONS Valencia, CA (661) Date: 01/31/12 Site name: UW Mobile Lab (Boulder-South) Start: 13:20 MST Operator: University of Wyoming Finish: 17:00 MST Project: University of Wyoming Audited by: David Yoho Witness: Brittni Emery Analyzer make: Thermo Model: 55i Serial No.: Filter: NA Sample flow: NA Span setting: NA Zero setting: NA Vacuum: NA Range: 5 PPM Last cal.: NA Methane PPM PPM PPM Audit Input DAS Dif Point (X) (Y) (%) NA Linear Regression: (Y=PPM Corrected, X=PPM Input) DAS Slope: Intercept: 0.02 Correlation: Comments: No problems noted. Certification Audit Equipment Make Model ID Date Dilution System: API M700EU 83 1/24/12 Zero Air System: API NA Calibration Gas: SMI Multi JJ /17/

59 AUDIT RECORD Avenue Hall Unit 9 OZONE Valencia, CA Date: 01/31/12 Start: 13:20 MST (661) Site name: UW Mobile Lab (Boulder-South) Operator: University of Wyoming Finish: 17:00 MST Project: University of Wyoming Audited by: David Yoho Witness: Brittni Emery Analyzer make: Thermo Model: 49i Serial No.: CM Filter: 02/01/10 Sample flow: 0.634/ lpm Ozone Measure: Span Set Point: Ozone Ref: Zero Set Point: -2.5 Last cal.: NA Range: ppm O3 PPM PPM PPM Audit Input DAS DAS Point (X) (Y) (Y) Linear Regression: (Y=PPM Corrected, X=PPM Input) DAS Slope: Intercept: Correlation: Comments: No problems noted. Certification Audit Equipment Make Model ID Date Dilution System: API M700EU 83 1/24/12 Ozone Standard: API M700EU 83 1/13/12 Zero Air System: API Ozone Transfer Standard Sample Freq: NA Cell Temperature: NA deg C Control Freq: NA Ambient Pressure: NA "Hg Span Setting: NA Certification Slope: Certification Intercept: ppm

60 AUDIT RECORD Avenue Hall Unit 9 TRACE LEVEL CARBON MONOXIDE Valencia, CA (661) Date: 01/31/12 Site name: UW Mobile Lab (Boulder-South) Start: 13:20 MST Operator: University of Wyoming Finish: 17:00 MST Project: WDEQ QA Audits Audited by: David Yoho Witness: Brittni Emery Analyzer make: Thermo Model: 48i-TLE Serial No.: NA Filter: NA Sample flow: NA Span setting: NA Zero setting: NA Vacuum: NA Range: 1 PPM Last cal.: NA CO PPM PPM PPM Audit Input DAS Dif Point (X) (Y) (%) NA Linear Regression: (Y=PPM Corrected, X=PPM Input) DAS Slope: Intercept: Correlation: Comments: No problems were noted. Certification Audit Equipment Make Model ID Date Dilution System: API M700EU 83 1/24/12 Zero Air System: API NA Calibration Gas: SMI Multi JB /07/

61 APPENDIX C Time Series 61

62 Figure C-1. Boulder South Road CH 4 time series for the period 10/29/ /02/2011. Figure C-2. Boulder South Road NMHC time series for the period 10/29/ /02/

63 Figure C-3. Boulder South Road NO x time series for the period 10/29/ /02/2011. Figure C-4. Boulder South Road NO time series for the period 10/29/ /02/