Reference: QBN1701-TCEQ-2007 Page 1 of 86

Date of Issue: 28 November 2007 Signed:

Checked by: Name: Melanie Williams for Managing Director Commercial in confidence

Measurements of VOC emissions from petrochemical industry sites in the Houston area using Differential Absorption Lidar (DIAL) during Summer 2007.
DRAFT FOR COMMENT



### FOR: Texas Commission on Environmental Quality

FOR THE ATTENTION OF : Russell Nettles

DATE OF TEST PERIOD: 16/07/07 to 18/08/07

AUTHORS: Rod Robinson, Tom Gardiner, Bob LipscombeCommercial in confidence

Reference QBN1701-TCEQ-2007 Page 2 of 85

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### Contents

Contents ....................................................................................................................... ............ 2
Introduction................................................................................................................... ........... 3Section 1. Measurements of VOC emissions from a Bulk Terminal, in the Houston nonattainment area. ............................................................................................................... ......... 4 Measurement description.................................................................................................. 4
Definition of VOCs............................................................................................................. 4
Measurements on the 16 th July. ........................................................................................ 6
Measurements on the 17 th July ......................................................................................... 8
Measurements on the 18 th July and 19 th July ................................................................ 10 Night-time measurements on the 20 th -21 st July. ............................................................ 11
Section 2 Measurements of VOC emissions fr om a Refinery in the Houston non-attainment

area........................................................................................................................... .............. 12 Measurement description................................................................................................ 12 Measurements of product storage tanks........................................................................ 14
Measurements of crude oil tanks.................................................................................... 16
Measurements of VOC emissions from coker C ........................................................... 24
Measurements of VOC emissions from heated oil tanks.............................................. 27
Measurement of VOC emissions from elevated flares.................................................. 28 Section 3 Measurements of Benzene emissions from Refinery........................................... 31 Measurement description................................................................................................ 31
Benzene concentration measurements on 17 th August. ................................................ 31
Measurements of benzene fluxes from the coker .......................................................... 36
Section 4. Measurements of SO 2 from the Sulphur Recovery Unit...................................... 38 Annex 1. Description of the DIAL technique........................................................................ 39 Overview of the Dial technique....................................................................................... 39 Description of the theory of Dial measurements........................................................... 39 Description of facility operated by NPL ........................................................................ 40
Calibration and validation .............................................................................................. 45 NPL open-path calibration facility................................................................................. 47 Annex 2 Speciated VOC measurements and Flux Correction Factors ................................. 48
Flux Correction Factors .................................................................................................. 48 Sampling Procedure......................................................................................................... 53 Analysis of the ATD tubes............................................................................................... 54 Annex 3. Meteorological Measurements .............................................................................. 65Reference: QBN1701-TCEQ-2007 Page 3 of 85

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## Introduction

This report presents the results of a m easurement campaign carried out using the NPL differential absorption LIDAR (DIAL) system at two petrochemical facilities in the The Houston non-attainment area region of South East Texas, between 16 th July to 18 th August 2007. The project was carried out for the Texas Commission on Environmental Quality (TCEQ). This report covers the measuremen ts undertaken by NPL, and does not cover
additional measurements undertak en by other contractors.

The primary objective of the study was to asse ss emission fluxes of VOCs and benzene from a number of identified potential sources, including st orage tanks, a delaye d coker unit, waste
water treatment areas and flares.

The report provides a summary of the VOC fluxes measured usi ng the DIAL technique at a
Bulk Terminal in the Houston non-attainment area (hereafter the Bulk Terminal) (Section 1) and a Refinery in the Houston non-attainment area (hereafter the Refinery) (Sections 2 and 3). Annex 1 provides an overview of the DIAL technique, and discusses the calibration and validation procedures. Annex 2 presents the results of speciation measurements of air samples, and Annex 3 presents a summary of the meteorological measurements undertaken during the campaign.Reference: QBN1701-TCEQ-2007 Page 4 of 85

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## Section 1. Measurements of VOC emissions from a Bulk Terminal, in the Housto n non-attainment area.

Measurement description.

DIAL measurements of the emissions of VOCs from storage tanks at the Bulk Terminal facility were carried out on 16 th , 17 th , 18 th , 19 th July and on the night of the 20 th -21 st July. The tanks selected by TCEQ/Bulk Terminal fo r measurement were naphtha storage tanks, numbers 22,23, 27, 28, and 29. Tank 3792 was also in cluded in some of the measurements, though no specific identifiable emissions were obse rved that could be at tributed to this tank.

Two measurement locations were used for th e DIAL measurements; these were both on Avenue H, the southern road within the plan t. The GPS coordinates for these measurement
locations were:

DIAL Location 1. North side of Ave H, due south of Tank 3770
29°21'23.64"N
94°55'2.82"W

DIAL Location 2 South side of Ave H, south of Tank 3792.
29°21'23.47"N
94°54'52.79"W

Measurements of VOC fluxes were carried out using the NPL DIAL as described in Annex 1. Fluxes were obtained by scanning the DIAL meas urement line-of-sight in vertical planes, downwind of the target emissions sources. Me asurements were also made upwind of the target sources to check for any upwind VOC fluxes. The measurement lines are shown in Figure 1.1.



### Definition of VOCs

The DIAL technique, as operated during these measurements, provides a measurement of mass emission in gasoline vapour equivalent. The DIAL measures VOCs by measuring the differential absorption of two wavelengths of light sensitive to hydrocarbons of C3 and
above.

This has been calculated for each air sample ta ken, and Annex 2 presents a set of correction
factors for each measurement location. For the measurements at the Bulk Terminal the factors range from between 0.8 to 1.6.Reference: QBN1701-TCEQ-2007 Page 5 of 85

Checked by: Figure 1.1.DIAL locations and scan lines used for VOC measurements at the Bulk Terminal.Reference: QBN1701-TCEQ-2007 Page 6 of 85

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### Measurements on the 16 th 

### July.

From Location 1, scans were made which measured the emissions from tanks 23,27,28,29
and 3792. Tank 22 emissions would also have been observed if these had been significant. Table 1.1 presents these results. The wind dir ection was generally from the SE, with speeds
of 3 to 6 m/s.

A small flux was measured, at a range consis tent with emissions from tanks 27, 28 and 23. This is shown in Figure 1.2. No observable em issions were seen from tank 22 or tank 3792. The average emission observed was 28 lbs/hr w ith a standard deviati on of ± 5 lbs/hr. It
should be noted the standard deviation of the results includes both the inherent uncertainty in the DIAL measurements and any real variabil ity in the emissions (whether due to source variability or variable dispersion).

Upwind scans (Scan IDs 16 and 21) gave results at or below the detection limit, which for the conditions prevailing at the Bulk Terminal was 1 lbs/hr.

Table 1.1. VOC fluxes measured on 16 th July at Bulk Terminal.

The DIAL provides a range resolved measurem ent of VOC concentrations. A DIAL scan can provide not only a measurement of the mass emissions flux, but also a visual indication of the location of the emission plume. Figure 1.2 shows an example of such a visualisation,
for Scan ID 12 on the 16 th July. The plot illustrates the vertical plane through which the DIAL scanned, and indicates the distribution of VOCs within this plume. The wind direction is indicated by the red arrow. The intensity of the colour plot is related to the concentration
of the VOCs. The maximum VOC con centration in this plot is 300 ppb.Reference: QBN1701-TCEQ-2007 Page 7 of 85

Checked by: Figure 1.2. Example of the VOC di stribution seen in a vertical scan at the Bulk Terminal (Scan 12, 16 th July). The green arrow represents the average wind direction. The peak VOC concentration observed in this scan was 300 ppb. DIALReference: QBN1701-TCEQ-2007 Page 8 of 85

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### Measurements on the 17 th 

### July

A further series of measurements were made of tanks 27,28,29 and 23 from Location 1. The wind was from the south, shifting slightly to so uth-westerly during the day with wind speeds ranging between 2.8 and 8.7 m/s. The results ar e presented in Table 1.2. The average flux
observed for these tanks on the 17 th July was 21 lbs/hr with a st andard deviation of ± 5 lbs/hr. Upwind scans were below the detectio n limit, indicating no contribution from other

sources.

In order to separate out and directly measure fluxes from tank 22, the DIAL was moved to Location 2, to the south of tank 3792. Scans coul d then be made isolating the emissions
from tank 22. It should be noted that this measurement confi guration is not ideal for flux measurements, as the measurement line of sight is very close to ta nk 22. Other locations were not possible due to constr uction work on the road to the north of tank 22. Scans made
from location 1 had indicated that the emissions observed from ta nk 22 were not significant. This was apparent because no significant co ncentrations were obs erved at ranges which would have been consistent with a plume from tank 22. Moving to a measurement line of sight further away from tank 22, to the north of Ave G, would have reduced the chance of measuring any small emissions from tank 22 due to dispersion. The fluxes observed, even close to tank 22, were very small, with an av erage flux of 3 lbs/hr a nd a standard deviation of 1.3 lbs/hr. The peak concentrations obser ved were less than 100 ppb, and these emissions would generally be considered insignifi cant in the context of a DIAL survey.

Table 1.2. VOC fluxes measured on 17 th July at the Bulk Terminal.Reference: QBN1701-TCEQ-2007 Page 9 of 85

Checked by: Figure 1.3. Example of a horizonta l scan showing the VOC dist ribution above naphtha tanks at the Bulk Terminal (Scan 17, 17 th July). The green arrow represents the average wind direction. The peak VOC concentration observed in this scan was 288 ppb.Reference: QBN1701-TCEQ-2007 Page 10 of 85

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### Measurements on the 18 th 

### July and 19 th 

### July

Further scans were made of tank 22 on both the 18 th and 19 th July, tables 1.3 and 1.4 present these data. The average emissions fluxes measured were 5 lbs/hr with a standard deviation
of 2.4 lbs/hr on the 18 th and 3 lbs/hr with a standard deviation of 2.4 lbs/hr on the 19 th

.

Two scans were made on the 18 th July to measure the emissi ons from tanks 23 and 28 from location 2. These scans may also have incl uded the contribution from tanks 29 and 22. However, the emissions from these tanks woul d be quite dispersed and are probably not
included in the measured fluxes. The scans are not ideal for flux determ ination, as the wind field would be very disturbed by the proximity of the tanks. Th e scans gave flux results that are much lower than those measured on the previous days for these tanks, with an average value of 3.5 lbs/hr. This indicates either, that the larger emissions originated from tank 27 (included in earlier measurements), and are not included in these scans. A more likely explanation, given subsequent measurements on the 19th, is that the wind field was not ideal and the scans did not capture the em issions from the tanks. On the 19 th July similar scans measured an average emission flux of 18 lbs/hr, which is consistent with the measurements
made on the 16 th and 17 th July for these tanks.

Table 1.3. VOC fluxes measured on 18 th July at the Bulk Terminal

Table 1.4. VOC fluxes measured on 19 th July at the Bulk TerminalReference: QBN1701-TCEQ-2007 Page 11 of 85

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### Night-time measurements on the 20 th 

### -21 st 

### July.

A series of measurements wa s made on the night of the 20 th -21 st July from Location 2, the results of these scans are given in Table 1.5 . These repeated the scans made from this location during the daytime. The wind was initia lly from further to the east, which was not ideal for this location, however it subsequently shifted furt her south, providing useable
measurements of tank 22 and tanks 23/28. The av erage emission flux measured from tank 22 was 1 lbs/hr, which is at the detection limit.

The measurements of the emissions from tanks 23 and 28 gave an average emission flux of 14 lbs/hr, with a standard deviation of 7 lbs/ hr. Although this emission is lower than that measured during the day. That, coupled with the variable wind pattern close to the tanks and the fact that the wind speed itself was lowe r during these measurements, suggests that
conclusions about the relations hip between day and night-time emissions cannot be drawn from these data, except to recognise that em issions are observed durin g the night-time, and therefore night time cannot be discounted from annualisation calculations based on day time

measurements.

A series of air samples, usi ng canisters and pumped sorbent tubes was also taken, and the results of these are reported in Annex 2. Figure A1.1 indicates th e locations of these samples at the Bulk Terminal.

Table 1.5. VOC fluxes measured on the night of 20 th July at the Bulk TerminalReference: QBN1701-TCEQ-2007 Page 12 of 85

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## Section 2 Measurements of VO C emissions from a Refinery in
the Houston non-attainment area.

Measurement description.

This section of the report describes the resu lts of measurements of VOC emissions from various sources within the Refinery. Measuremen ts of VOC emissions were carried out from
the 25 th July to the 11 th August. Table 2.1 lists the meas urements days and the sources monitored on each day. The DIAL measurement locations are identified on individual maps in the following Sections.

Date DIAL Location Sources monitored 25th July Refinery Location 1 Product tanks
26 th July Refinery Location 1 Product tanks
28 th July Refinery Location 2 Crude oil tanks, coker
29 th July Refinery Location 2 Crude oil tanks
30 th July Refinery Location 3 Gasoline tanks and flare 6
31 st July Refinery Location 2, 2C Crude oil tanks and coker 1st August Refinery Location 2 Coker
2 nd August Refinery Location 4 Waste water treatment and
crude oil tanks
3 rd August Refinery Location 2 Coker
5 th –6 th August (Night) Refinery Location 2 Crude oil tanks

6 th – 7 th August (Night) Refinery Location 3 Gasoline tanks, coker and
flare 6

7 th – 8 th August (Night) Refinery Location 5,6,7 Product tanks
Hot oil tanks
9 th August Refinery Location 8 Flares
10 th August Refinery Location 8 Flares
11 th August Refinery Location 8 Flares

Table 2.1 Summary of DIAL VOC fl ux measurements at the Refinery

The GPS positions for the DIAL locations were:

Refinery Location 1 By Muster Point 8
29°22'1.48"N
94°56'23.11"W

Refinery Location 2

E 4 th street, next to tank 1020 29°22'4.56"N
94°55'13.56"WReference: QBN1701-TCEQ-2007 Page 13 of 85

Checked by: Refinery Location 2C
Further north on E 4 th street 29°22'5.58"N
94°55'14.09"W

Refinery Location 3 Avenue J, North of tank 1045
29°22'10.26"N
94°55'29.40"W

Refinery Location 4 Avenue N, south of Surge Basin 2
29°21'52.38"N
94°55'17.22"W

Refinery Location 5
Outside Gate 16
29°22'3.78"N
94°56'27.42"W

Refinery Location 6
On W 4 th St, by tank 17
29°22'21.36"N
94°56'10.98"W

Refinery Location 7 Avenue G, south of ARU
29°22'23.52"N
94°56'15.36"W

Refinery Location 8 Grant Avenue, South of tank 20.
29°22'35.45"N
94°56'29.47"W

The measurement results are presented in th e following sections, grouped by the sources measured. It is important to note that the potential emission sources measured were identified by TCEQ and the refinery, and m easurements were focussed on these sources. This study did not include a full survey of all sources within the refinery, and was not aimed at determining total refinery emissions.Reference: QBN1701-TCEQ-2007 Page 14 of 85

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### Measurements of pro duct storage tanks.

A small number of distillate pr oduct storage tanks were identifie d as being of interest. These
included tanks 55 and 53. Scans were made of these tanks on the 25 th 26 th July and during the night of 7 th August. These measurements were made from Location 1 on the 25 th and 26 th

and from Location 5 on the 7 th August. The results are presented in Table 2.2. The emissions from tank 55 were not significant, with averag e emission fluxes measured of 5 lbs/hr (not counting the negligible fluxes measured during very low a nd variable wind conditions). Upwind scans were in general below the detection limit, how ever one scan down Avenue K and upwind of the hydrogen plants No.1 and No.2 measured a small flux of 7 lbs/hr. Measurements of tank 55 during the evening of the 7 th August showed similar emission fluxes, with an average of 6 lbs/hr. Tank 57 wa s too close to the DIAL to enable it to be
measured on the 7 th August. Measurements of tank 53 we re made during the evening of the
7 th August and an average flux of 24 lbs/hr w ith a standard deviation of 8 lbs/hr was measured. Upwind measurements were below detection limits.

Table 2.2 Measurements of VOC fl uxes from product storage tanksReference: QBN1701-TCEQ-2007 Page 15 of 85

Checked by: Figure 2.1. DIAL locations and scan lines used for DIAL measurements of VOC emission fluxes from the product storag e tanks at the Refinery.Reference: QBN1701-TCEQ-2007 Page 16 of 85

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### Measurements of crude oil tanks

A series of measurements of the emissions fr om the crude oil storage tanks was made over several days. Measurements were made on the 28 th 29 th 31 st July, 2 nd August and on the night of the 6 th August. The results of measurements of different tanks are summarised in Table 2.3, all flux results ar e presented in Table 2.4.

Measurements were made from Location 2, ap art from the measurements of tanks 1020 and
1021 on the 31 st July, for which the DIAL wa s moved north to Location 2C.

Tanks Average emission flux
Lbs/hr
1020 <2
1021 16
1024 5
1025 11
1052 22 28 th July
39 2 nd August
24 5 th August, Night
1053 7
1055 <5

Table 2.3 Summary of VOC fluxe s from crude storage tanks

In order to assign emission fluxes to individual tanks, some interpretation of the flux results
in Table 2.4 has had to be made. In some cas es, flux measurements were made which were
downwind of a number of tanks. Where these tanks were also measured separately on other occasions then the split of th e flux between the possible sources has been made based on
these individual measurements. For the measurements made on the 2 nd August from Refinery Location 4, the measurements of tanks 1055 and 1053 probably include a component of the emissions observed from tank 1052. The flux is not significantly higher than that measured from tank 1052 alone, and so it is clear there is no significant emission
flux from either tank 1055 or ta nk 1053. This is cons istent with the prev ious measurements of these tanks, which did not include emissions upwind from tank 1052. Similarly
measurements of tanks 1020 and 1021 on the 29 th July may have included some emissions from tanks 1025 and 1024, however, the wind direc tion was such that this is unlikely. The wind direction, and location of th e observed flux, also indicate that most of the observed
emission flux is attributable to tank 1021, and so the average emissions have been assigned to tank 1021. This is supported by measurement of tank 1020 only, on the 31 st July, which gave very low fluxes, many below 1 lbs/hr.

No significant emissions were observed from tank 1055, which was in the near field during
a number of scans.

In summary, most of the tanks observed during these measurements did not have significant emission fluxes, and in general, the emission fluxes from indivi dual tanks were < 10 lbs/hr.Reference: QBN1701-TCEQ-2007 Page 17 of 85

Checked by: A VOC emission was observed from tank 1052, with an average emission of 39 lbs/hr
observed on the 2 nd August.

Figure 2.2.DIAL locations and scan lines used for DIAL measuremen ts of VOC emission fluxes from the crude oil tanks at the Refinery.Reference: QBN1701-TCEQ-2007 Page 18 of 85

Checked by: Table 2.4 Measurements of VOC fl uxes from crude oil storage tanksReference: QBN1701-TCEQ-2007 Page 19 of 85

Checked by: Table 2.4 (continued) Measurements of VOC fluxes from crude oil storage tanksReference: QBN1701-TCEQ-2007 Page 20 of 85

Checked by: Measurements of gasoline tanks and flare 6.

Measurements of gasoline storage tanks 501, 502, 503, and 504 were carried out from
location 3 on the 30 th July and on the night of the 6 th August. The results are presented in
Table 2.5.

The wind directions for these measurements we re not ideal for flux determination; however, any significant emissions would have been observed. Upwind measurements from location 3
included measurements of emissions from flare 6, which was operational during the measurement periods. As can be seen from th e results presented in Table 2.5, there was no significant VOC flux observed from these tanks; the measurements are consistent with an emission of approximately 5 lbs/hr from indi vidual tanks. Night time measurements found slightly lower emissions; however as these meas urements were close to the detection limit, drawing any conclusion from these results about night versus day emissions is not recommended. Owing to the wind direction during the night time measurements, it is also likely these scans would not have fu lly captured emissions from tank 502.

Measurements of emissions from flare 6 on the 30 th July gave an average flux of 4 lbs/hr. During the night time measurements on the 6 th August, an average flux of 22 lbs/hr was
measured from flare 6.

It should be noted that these emissions could act as an upwind source for the gasoline tank measurements. However, they were spatially separated from the emissions from the gasoline
tanks and were not included in these measured fluxes. Therefore this upwind source did not
have to be subtracted from the tank measuremen ts, which can lead to a significant source of uncertainty and is something th at is avoided if possible.

Table 2.5 Measurements of VOC fluxes from gasoline storage tanksReference: QBN1701-TCEQ-2007 Page 21 of 85

Checked by: Figure 2.3. DIAL locations and scan lines used for DIAL measurements of VOC emission fluxes from the gasoline tanks at the Refinery.Reference: QBN1701-TCEQ-2007 Page 22 of 85

Checked by: Measurements of Water Treatment area.

Measurements were made of the water treatment plant on the 2 nd August. Measurements
were also made of crude tanks on this day and these have b een reported in the relevant
Section above.

The emissions fluxes observed from the waste treatment areas are given in Table 2.6. The average flux seen from the waste water treatment area, and specifically from the west side of the secondary and tertiary effluent treatment facilities, was 30 lbs/hr . Scans upwind of the water treatment plant measured less than 1 lb s/hr. Two scans were also made of the flux from the API separator located at the NE co rner of Surge Basin 2, and these measured a small average emission flux of 7 lbs/hr.

Table 2.6 Measurements of VOC fluxes water treatment areas

Figure 2.4. DIAL locations and scan lines used for DIAL measurements of VOC emission fluxes from the waste water treatment areas at the Refinery.Reference: QBN1701-TCEQ-2007 Page 23 of 85

Checked by: Figure 2.5. Example of the VOC dist ribution seen in a vertical scan at the Refinery (Scan 285). This scan measured the VOC emissions from tank 1052. The green arrow represents the average wind direction. The peak VOC concen tration observed in this scan was 495 ppb. DIAL Tank
1052Reference: QBN1701-TCEQ-2007 Page 24 of 85

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### Measurements of VOC em issions from coker C

Measurements were made of the VOC emissions from the operating coker, unit C, on the
28 th July, 31 st July, 1 st 3 rd August.

It had been suggested that re finery coker units could be a significant source of emissions, and figures of several hundred lbs/hr were discussed. One of the primary aims of these
measurements was therefore to determine if the emissions from this coker were of a similar level. Over a number of measurement days, with different conditions, and through several cycles of the coker, the highe st emission flux observed during a DIAL scan from the coker
was 44 lbs/hr

The average emission fluxes observed from th e coker are given in Table 2.7, and all
individual flux results ar e presented in Table 2.8.

Date Average emission flux from
coker Average upwind flux

28 th July 10 lbs/hr 2 lbs/hr
31 st July 31 lbs/hr 3 lbs/hr
1 st August 12 lbs/hr 4 lbs/hr
3 rd August 32 lbs/hr 8 lbs/hr

6 th August - Night 4 lbs/hr N/A

Table 2.7, Summary of VOC emissions fluxes measured from Coker ‘C’

Measurements upwind of the cokers identified some small fluxes intermittently on the 31 st July and 3 rd August. These presumably arise from process units close to the cokers, including potentially, the coker vapour recovery unit. These upwind concentrations have not
been subtracted from the observed coker re sults, however, their potential impact on the uncertainty of the results should be considered.

During the coker measurements on the 3 rd August a small, localised emission was observed
south of tank 1010. This was consistent with em issions from waste water vent pipes, located
at the north end of E-4 th street. The average emission flux ob served from this source was 9
lbs/hr.Reference: QBN1701-TCEQ-2007 Page 25 of 85

Checked by: Figure 2.6.DIAL locations and scan lines used for DIAL measuremen ts of VOC emission fluxes from coker C at the Refinery.

Figure 2.7. Example of the VOC dist ribution seen in a vertical scan at the Refinery (Scan 263), downwind of coker C. The green arrow represents the average wind direction. The peak VOC concentration observed in this scan was 234 ppb.Reference: QBN1701-TCEQ-2007 Page 26 of 85

Checked by: Table 2.8. Measurements of VOC em ission fluxes from coker ‘c’.Reference: QBN1701-TCEQ-2007 Page 27 of 85

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### Measurements of VOC emissi ons from heated oil tanks

A small number of heated tanks containing fu el oil were measured. These tanks were monitored on the night of the 7 th August. The emissions from two tanks 43, and 60 were measured, and the results are given in Table 2.9.

The average emission flux from Tank 43 was 6 lbs/hr and from Tank 60 the average emission flux was 9 lbs/hr. Upwind fluxes were less than 1 lbs/hr. These results show the emissions from these tanks are very low an d they are not signifi cant sources of VOC
emissions.

Table 2.9. Measurements of VOC emission fluxes from hot oil tanks.

Figure 2.8. DIAL locations and scan lines used for DIAL measurements of VOC emission fluxes from the hot oil tanks at the Refinery.Reference: QBN1701-TCEQ-2007 Page 28 of 85

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### Measurement of VOC emissions from elevated flares.

Measurements of a temporary flare stack locate d in the NW corner of the refinery were undertaken. This flare had a very visible flame, and the aim wa s to determine any emission due to incomplete combustion in the flare. The DIAL was located in Grant Avenue and measured downwind and upwind of the fl are to identify any plume of un-burnt hydrocarbons. These measurements identified very low levels of hydrocarbon downwind of the flare, and the VOC emission flux measured from this flare was ~ 6 lbs/hr. This is not surprising given that the flare was reported to be mainly burning hydrogen.

However, during the measurement of the temp orary flare, a high concentration VOC plume was observed at a closer range than the tem porary flare stack. This plume was consistent with emissions from another elevated flare, the ULC flare. This flare had an almost invisible flame during daylight, but was observed to be lit at night. Table 2.11 lists all the measured fluxes from these flares, and Table 2.10 provide s a summary of the emissions from the ULC
flare.

Date Average VOC emission flux
9 th August 147 lbs/hr
10 th August 167 lbs/hr
11 th August 263 lbs/hr

Table 2.10 Summary of measurements of VOC emissions from ULC flare.

The measurements of the ULC plume showed a fairly high degree of variability, and this will be due to a combination of variability in the flare emissions and the possibly to movement of the narrow plume duri ng the period of each DIAL scan.Reference: QBN1701-TCEQ-2007 Page 29 of 85

Checked by: Figure 2.9. DIAL locations and scan lines used for DIAL measurements of VOC emission fluxes from flare stacks at the Refinery

Figure 2.10 Example of the VOC dist ribution seen in a vertical scan at the Refinery (Scan 432) downwind of the ULC flare. The green arro w represents the aver age wind direction. The peak VOC concentration observed in this scan was 3.86 ppm.Reference: QBN1701-TCEQ-2007 Page 30 of 85

Checked by: Table 2.11. Measurements of VOC flux from ULC and temporary flares.Reference: QBN1701-TCEQ-2007 Page 31 of 85

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## Section 3 Measurements of Be nzene emissions from Refinery

Measurement description

Measurements of benzene were carried out on the 17 th and 18 th August 2007 at the Refinery. Measurements were made of the Aromatic Recovery Unit (ARU) on the 17 th and the operational Coker (Coker Unit C) on the 18 th . Measurements on the 17 th were carried out in parallel with a UV Open Path DOAS spectrometer, operated by the EPA and were made for comparison purposes. Measurements on the 18 th were carried out to obtain emissions flux measurements from the coker operations, and we re timed to include the period during which the unit was cutting coke.



### Benzene concentration measurements on 17 th 

### August.

The measurements on the 17 th August were carried out to compare the concentrations measured by DIAL with those obtained by the open-path UV-DOAS system operated by Cary Secrest from EPA. Both systems were set up to measure a 200m path close to the ground, downwind of the ARU. Figure 1 shows th e DIAL and DOAS locations and also the locations of 2 air samples, which were take n during the tests. The DIAL was located in Avenue C, South of Tank 5, GPS locati on 29°22'35.28"N, 94°56'2.10"W. The wind was
from directions between 130° to 170° from N, at speeds of between 6 mph to 16 mph.

Figure 3.1, Location for measurements of benzene concentrations from the ARU

During these measurements the DIAL beam was ke pt at a fixed line of sight, in a similar configuration to the UV-DOAS, and not scanned to obtain concentration profiles. Therefore, benzene fluxes were not determined. The two measurement-paths for the DIAL and the UV-Reference: QBN1701-TCEQ-2007 Page 32 of 85

Checked by: DOAS were as close as was logistically possibl e. The DIAL data were processed to assess the total integrated concentration over the assigned path. The path length of the DOAS was stated by the EPA operators to be from 247 m to 440m from the DIAL. The ARU unit was measured from the site map to be 100m l ong from 280 to 380 m from the DIAL. The DIAL and UV-DOAS results are plotted for comparis on in Figures 2 and 3. The DIAL results are tabulated in Tables 1 and 2. The results plot ted for the UV-DOAS are as supplied by Cary Secrest (US EPA). There is no difference betw een the UV-DOAS results in figures 2 and 3, only the DIAL pathlength has been varied, the UV-DOAS pathlength is a fixed parameter dependant on the instrument configuration. Th e DIAL results shown in the tables are the averages of a number of measurements taken during the periods indica ted, and the standard
deviations of the concentrations is also given. Where no standard deviation is given this is because the result is for a single measurement.

Table 3.1, DIAL results – ppb benzene determin ed over a 193m path comparable to the UVDOAS.Reference: QBN1701-TCEQ-2007 Page 33 of 85

Checked by: Table 3.2, DIAL results – ppb benzene determined over a 100m path comparable to the
extent of the ARU.

Air samples were taken in canisters and with pumped sorbent tubes, at the locations shown in Figure 1. Table 3 shows the results of the an alyses of these canisters for benzene. The samples were taken between 17:29 and 18:29 fo r the EPA line of si ght and 17:53 and 18:53 for the DIAL line of sight.

Table 3.3, Air sample analyses for ARU measurements.

The concentrations of benzene measured usi ng the pumped sorbent tubes are similar to the
levels measured with both the UV-DOAS and the DIAL. The concentrations measured by
the DIAL are close to the limit of detection for the DIAL system and the standard deviations
of the results reflects this. Benzene Toluene Ethylbenzene m/p-Xylene o-Xylene
Tubes Canisters Tubes Canisters Tubes Canisters Tubes Canisters Tubes Canisters

ARU ppb ppb Ppb ppb ppb Ppb ppb ppb ppb ppb
DIAL LOS 12.87 <2.00 18.79 12.26 2.33 2.04 9.36 5.51 3.05 <2.00
DOAS LOS 6.71 <1.88 9.79 20.52 1.90 2.46 5.29 8.49 1.44 2.59Reference QBN1701-TCEQ-2007 Page 34 of 85Checked by:Figure 3.2, Comparison of DIAL and UV-DOAS benzene concentrations. DIAL integrated path corresponding to reported UV-DOAS 193mpathlength.Reference: QBN1701-TCEQ-2007 Page 35 of 85Checked by:Figure 3.3, Comparison of DIAL andUV-DOAS benzene concentrations. DIAL results for 100m path corresponding to the location oftheARU unit.Reference QBN1701-TCEQ-2007 Page 36 of 85

Checked by: 

### Measurements of benzene fluxes from the coker

Measurements were made of the benzene concen trations downwind of coker, unit C, during the operation of this coker on the 18 th August. The measurements were carried out from 17:20 to 20:45. The coker was cutting coke between 19:50 and 20:38.

The configuration of the measurements and location of the DIAL during these measurements is shown in Figure 4Reference: QBN1701-TCEQ-2007 Page 37 of 85

Checked by: Figure 3.4. Location of DIAL for measurements of benzene fluxes from coker Unit C. The DIAL was located on Avenue J, to th e west of Tank 1010, at GPS coordinates 29°22'10.98"N, 94°55'19.50"W. The wind during th e measurements was from directions between 125° to 143° from N, with speeds be tween 6 mph to 9 mph. Vertical scans were made downwind of the coker; sc ans were also made upwind of the coker to check for any other sources of benzene. The results are give n in Table 4. During most of the period of
measurements the DIAL values are at or belo w the detection limits. For these measurements, the detection limits, in terms of lbs per hr fl ux, were of the order of 0.5 to 1 lbs per hr. During the period before the coker commence d cutting, the fluxes measured were often below the detection limit and have been reported as 0 lbs per hr. In some cases, a figure of less than a given flux is reported. In these case s, a detectable concentration was recorded, but the uncertainty in the results is such that only an upper limit is reported. Detected concentrations of benzene were in general ar ound 0.1 ppm. During the coker cut, a small but observable flux of benzene was measured, the tw o results giving fluxes of 1.5 lbs per hr and 2.1 lbs per hr. Upwind scans showed no significant source of benzene.

The results of the analyses of the air samp le taken downwind of th e coker are shown in Table 5. This sample was taken during the period of the coker cut, and a low concentration of benzene ~ 1 to 2 ppb was measured.

Table 3.4. Measured fluxes during coker operation.

Table 3.5, results of air sample analyses downwind of coker. Benzene Toluene Ethylbenzene m/p-Xylene o-Xylene
Tubes Canisters Tubes Canisters Tubes Canisters Tubes Canisters Tubes Canisters

ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb
Downwind Coker 1.33 <2.00 0.61 2.11 0.44 <2. 00 0.49 <2.00 <0.3 <2.00Reference: QBN1701-TCEQ-2007 Page 38 of 85

Checked by: 

## Section 4. Measurements of SO 2 

## from the Sulphur Recovery
Unit

A series of measurements was carried out on the 14 th August to measure the SO 2 flux from the Sulphur Recovery Unit wet gas scrubber plum e. Close to the stack this appeared as a visible plume, mainly consisting of water va pour. The measurements were made through the plume, roughly at the point at which it became invisible to the unaided eye. The enhanced backscatter from the plume was used to check that the scans did intercept the plume. The aim of the measurements was to compare the measured flux with an emission rate
determined from the stack flow rate and measurements of the stack gas SO 2 concentration
determined from an installed continuous emi ssions monitor. However, prior calculations indicated that the likely concentration within the plume would be at or below the DIAL detection limit, and this was found to be th e case. The average flux measured by the DIAL was 0.003 lbs/hr, with a standard deviation of 0.008 lbs/hr. Table 4.1 lists the measured SO 2 fluxes.

Table 4.1. Measurements of SO 2 flux from SRU.

The DIAL location was:

Refinery Location 13 Avenue F, north of flare 5.
29°22'28.42"N
94°54'54.56"WReference: QBN1701-TCEQ-2007 Page 39 of 85

Checked by: 

## Annex 1. Description of the DIAL technique.

Overview of the Dial technique

The Differential Absorp tion Lidar (DIAL) technique is a laser-based remote monitoring technique which enables range-resolved concentr ation measurements to be made of a wide range of atmospheric species. Th is section explains the theory of the DIAL technique and describes the NPL system in detail.



### Description of the theory of Dial measurements

The atmospheric return signal meas ured by a DIAL system is gi ven by the Light Detection and Ranging (Lidar) equation, a simplified fo rm of which is give n in Equation 1.

where D
x is a range independent constant, C(r) is the concentration of an absorber with absorption coefficient α x and A
x (r) is the absorption coefficien t due to all other atmospheric absorption, E
x is the transmi tted energy and B
x is the backscatter coeffi cient for the atmosphere at wavelength x.

The equation has three basic components:

- a backscatter te rm based on the strength of th e signal scattering medium - parameters associated with the DIAL system
- a term which is a me asure of the amount of absorption of the signal whic h has occurred due to the presence of the target species.

In the DIAL technique, the laser is operated alternately at two adjacent wavelengths. One of these, the "on-resonant wavelength", is chosen to be at a wavelength which is absorbed by the target species. The other, the "off-resonant wavelength", is chosen to be at a wavelength which is not absorbed significantly by the target species.

Pairs of on- and off-re sonant signals are then acquired and averaged separately until the required signal to noise ratio is achieved.

The two wavelengths used are close together, hence the atmospheric terms A
x (r) and B
x (r) in the lidar equation can be assume d to be the same for both wa velengths. These terms are then cancelled by taking th e ratio of the two returned signals.

The path-integrated concentra tion (CL) may be derived (Equation 2) by multiplying the logarithm of the ratio of the si gnals by the ratio of the absorpti on of the two wavelengths by the target species. x x x

2 x

0 r

x x P (r)= E D

r B (r) {-2 [ A (r )+ C(r )]d r} exp 

## ∫ ′ ′′ α (1)Reference: QBN1701-TCEQ-2007 Page 40 of 85

Checked by: where N is the number of pulse pairs averaged, Δα = α OFF - α ON is the differential absorption coefficient and S represents the received power after normalisation for th e on- and off-resonant signals respectively.

This path-integrated concentration represents the total concentration of th e target species in the atmosphere along the measured line- of-sight out to the range r.

The range-resolved concentration can then be derived by differentiati ng the path-integrated concentration (Equation 3).

where C(r) is the point concentration at range r along the line-of-sight.



### Description of facility operated by NPL

The DIAL system operated by NPL is housed in a mobile la boratory. It can operate in the infrared and ultraviolet spectra l regions allowing coverage of a large number of atmospheric species. A scanner system directs the output beam and detection optics, giving almost full coverage in both the horizontal and vertical planes.

The system also contains anc illary equipment for meteorologi cal measurements, including an integral 10 m meteorological mast with wind speed, direction, temperature and humidity

measurements.

The system is fully self contained, with power provided by an on board generator, and has full air conditioning to allow operation in a range of ambient conditions.

The following sections describe the DIAL system in more detail.

Source The source employs a combination of Nd-YAG and dye lasers toge ther with vari ous non-linear optical stages to generate the tuneable infrared and ultraviolet wavelengths. The source has a pulse repletion rate of 10 Hz an d an output laser pulse duration of ~10 ns. A small fraction of the output beam in each channel is split off by a beam splitter and meas ured by a pyroelectric detector (PED) to provide a value for the tran smitted energy with wh ich to normalise the
measured backscatter return.

Detection The returned atmospheric backscatter signal is co llected by the scanning telescope. This directs the collected light into separate paths for th e infrared and ultravio let lidar channels. The CL(r)= 1

2 1

N S (r)

S (r) i=1 N ON,i

OFF,i Δ α 

# ∑ log (2)

C(r)= dCL(r)

dr (3)Reference: QBN1701-TCEQ-2007 Page 41 of 85

Checked by: returned light passes through band pass filters re levant to each detection channel and is then
focused onto the detection elements. Solid-state cryogenically-cooled detectors are used in the infrared channel and low-noise phot omultipliers in th e ultraviolet.

After amplification the signals from these detectors are digiti sed using high speed digitisers. The digitisers are clocked using a clock genera tor triggered by an optical detector in the transmission chain. This ensures the range gati ng is correctly synchronised to the laser pulse transmission. The signals from the PED monitoring the transmitted energy are also digitised
and stored.

Data Analysis The data acquired are analysed, using the DIAL techniques described below, to give the rangeresolved concentration al ong each line-of-sight.

The data analysis process cons ists of the following steps :

i) Background subtraction Any DC background value is subtracted from the signals. This measured background takes account of any DC signal offset which may be present due to electronic offsets and from incident background radiation. The background level is derived from the average value of the far field of the returned lidar signal wh ere no backscattered light is present.

ii) Normalisation for varia tion in transmitted energy The two signal returns are normalised using th e monitored values of the transmitted energy. The mean transmitted energy is used to norma lise the averaged return signal. For this application, this has been s hown to be equivalent to norm alising individual shots against transmitted energy and then averaging the normalised values.

iii) Calculation of path-integrated concentration The path-integrated concentration of the target species, out to the range r, is calculated by multiplying the log of the ratio of the returned no rmalised signals by the differential absorption.

The absorption coefficients used in this calculation are derived from high-resolution spectroscopy carried out using re ference gas mixtures at NPL.

iv) Derivation of range- resolved concentrations.
In order to better visualise th e data the integrated concentr ation profiles are piecewise differentiated to give the range-resolved concentration along the line-of-sight.

v) Calculation of emission fluxes Range-resolved concentration measurements al ong different lines-of-sight are combined to generate a concentration profile. This is carried out using algo rithms developed at NPL which
reduce artefacts due to the difference in data density at different ranges, due to the polar scanning format of the data. Th e emission flux is then determined using the concentration profile together with meteorological data.

The emitted flux is calcu lated using the followin g mathematical steps:-Reference: QBN1701-TCEQ-2007 Page 42 of 85

Checked by: (a) The product is form ed of the gas concentr ation measured with the DIAL technique at a given point in space, and the component of the wind velocity pe rpendicular to the DIAL measurement plane at the same location.

(b) This product is computed at all points within the measured conc entration profile, to form a two-dimensional array of data.

(c) This array of results is then integrat ed over the complete co ncentration profile to produce a value for th e total emitted flux.

Considerable care is needed in applying the meteorological data, particularly when the concentration profile measured by the DIAL tech nique has large and complex spatial variations since, for example, errors in the wind speed in regions where large conc entrations are present will significantly affect the accurac y of the results. In such case s, a more complex procedure is used which employs a further software pack age to combine the da ta from the set of
anemometers with that of an additional meteorol ogical model, to genera te the complete wind field over the concentration profile. This mode l calculates the variation of wind speed with height, as a function of various parameters (such as the roughness of the terrain). The calculated
wind field is then combined wi th the measured gas concentra tion profile using the procedure
described above.

A summary of the ultraviolet and infrared performance capabilities of the NPL DIAL facility are given in Tables A1.1 and A1.2. Th e values given in these tables are based on the actual levels of performance of the system obtained during field measurements, rather than
calculations based on theoretic al noise performances. For simplicity the numbers are presented as a single concentration sensitiv ity and maximum range values. However, the detailed performance behaviour of a DIAL syst em is much more complex and there are a number of key points th at should be noted :

• The DIAL measurement is of concentrat ion per unit length rather than just concentration. So the sensitivity applies for a specified pathlength – 50 metres in this case. Measurements over a shorter path woul d have a lower sensitivity, and would be more sensitive over a longer path.

• Since the backscattered lidar signal varies with range, generally following a (range)- 2 function, the sensitivity is a function of range. The sens itivity values given in the table apply at a range of 200 metres, a nd these will get poorer at longer ranges.

• The maximum range of the system is ge nerally determined by the energy of the emitted pulse and the sensitivity of the detection system, except in the case of nitric oxide where range is limited by oxygen ab sorption at the short ultraviolet wavelengths required for this species.

• In all cases the performance parameters are based on those obtained under typical meteorological conditions. For the ultrav iolet measurements the meteorological conditions do not have a great effect on the measurements as the backscattered signal level is predominantly determined by mol ecular (Rayleigh) scattering, and this does not vary greatly. However, in the infrar ed the dominant scattering mechanism is from particulates (Mie scattering). So the si gnal level, and therefore the sensitivity, is dependant on the particular loading of the atmosphere, and this can vary dramatically over relatively short timescales.Reference: QBN1701-TCEQ-2007 Page 43 of 85

Checked by: The NPL DIAL has a theoretical range resoluti on of 7 metres along the measurement beam,
and a vertical or horizontal scan resolution which can be le ss than 1 metre at 100 metres. However, the actual range resolution determined by the signal averagin g used, will depend on atmospheric conditions and th e concentration of the measured pollutant, and may be of
the order of 30 m.

The DIAL is able to make measurements of a wide range of compoun ds, including benzene and other aromatics, individual VOCs and total VOCs, see Tables 2a and 2b. The methodology for obtaining measurements of the total VOC content from C3 to C15 is provided below. It consists of the combina tion of DIAL measurements with air sampling and GC analysis. The system is able to monitor individual aromatic compounds and VOC species, which have absorption features in the IR and UV spectral regions covered by the DIAL system. NPL has the spectral expertis e, access to spectral libraries and in-house spectroscopic capability to assess the DIAL sensitivity for additional individual species.

The general hydrocarbon measuremen t listed in Table A1.2 uses an infrared absorption that is common to all hydrocarbons with three or more carbon atoms, linked to the stretch frequency of the carbon-hydrogen bond. As such it provides a measure of the mixture of volatile organic compounds (VOCs) that are present at an oil or petrochemical site. The pair of infrared wavelengths used for this DIAL measurement are selected so that the absorption per unit mass is relatively invari ant with respect to the mix of different hydrocarbons that are present. However, the sensitivity of this measurement in terms of ppb of hydrocarbon depends on the mixture of speci es present, and the value given in the table reflects the typical mix of hydrocarbons found at oil refineries.

Although the general hydrocarbon measurement provides a good estimate of the overall amount of hydrocarbons present, the accuracy of this measurement can be improved, and the total VOC concentration calculated, by combini ng the DIAL measurements with the results of gas chromatography (GC) analysis of the em itted gases. The standard procedure for this involves taking whole air samples around th e site in locations where the DIAL measurements show the emitted plumes are present. The VOCs present in these samples are identified and quantified by GC analysis. The results provide the relative levels of all the VOCs present with a con centration of 0.1 ppb or higher. Th e results of this analysis are combined with NPL’s unique spectral library of quantified infrared absorptions of an
extensive set of VOCs to calculate the comb ined absorption coefficient for the actual VOC mixture present at the site. A ppling this absorption coefficient to the DIAL results enables
the total VOC emission rates to be calculated.Reference: QBN1701-TCEQ-2007 Page 44 of 85

Checked by: Species Sensitivity (1) Maximum range (2)

Nitric oxide 5 ppb 500 m
Sulphur dioxide 10 ppb 3 km
Ozone 5 ppb 2 km
Benzene 10 ppb 800 m

Toluene 10 ppb 800 m Table A1.1 Ultraviolet capabi lity of NPL DIAL Facility

Species Sensitivity (1) Maximum range (2)

Methane 50 ppb 1 km

Ethane 20 ppb 800 m
Ethene 10 ppb 800 m
Ethyne 40 ppb 800 m
General hydrocarbons 40 ppb 800 m

Hydrogen chloride 20 ppb 1 km
Methanol 200 ppb 500 m

Nitrous oxide 100 ppb 800 m Table A1.2 Infrared capability of NPL DIAL Facility

Note 1. The concentration sens itivities apply for measurements of a 50 metre wide plume at a range of 200 metres, under typical meteorological conditions.

Note 2. The range value represents the typi cal working maximum range for the NPL DIAL system.Reference: QBN1701-TCEQ-2007 Page 45 of 85

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### Calibration and validation

The NPL DIAL system has several in-built calibration tech niques and proce dures. The most important are the in-line gas calibration ce lls. The gas cells ar e filled with known concentrations of the target species, from NPL standard ga s mixtures, which are directly
traceable to national standards. A fraction of the transmitted be am is split off and directed through a gas cell to a PED, in the same way as the beam for th e transmitted energy monitors. This provides a direct measurement of the differ ential absorption at the operating wavelengths by the target gas. The transmission through the gas cells is continuously monitored during the operation of the system to detect any possible drift in the lase r wavelengths. Th e system also employs a wavemeter to monitor the wavelengths transmitted duri ng operation. Th e calibration cells are also periodically placed in the output beam to show the concentration response of the whole system is as expected.

A number of field comparisons have been undertaken to de monstrate the accuracy of the measurements obtained with DIAL. Examples of these carried out by NP L are detailed below:

i) Intercomparisons have been carried out in the vicinity of chem ical and petrochemical plants where a large number of different volat ile organic species are present. In these intercomparisons, the DIAL ra diation was directed along the same line of sight as a line of point samplers. The point samplers were operated either by drawing air into internally-passivated, evacuate d gas cylinders or by pumpin g air at a known rate, for a specified time, through a series of absorp tion tubes which efficiently absorb all hydrocarbon species in the range C 2 - C 8 . The results obta ined for the total
concentrations of VOC s measured by the po int samplers and those measured by the infrared DIAL technique agre ed within ± 15%. The con centrations of atmospheric toluene measured by the ultraviolet DIAL sy stem agreed with th ose obtained by the point samplers to within ± 20%.

ii) The ultraviolet DIAL syst em was used to monitor the fluxes and concentrations of sulphur dioxide produced from combustion a nd emitted by industrial stacks. These
stacks were instrumented with calibrated in-s tack sampling instruments. The results of
the two sets of measurements agreed to within ± 12%.

iii) DIAL Measurements of c ontrolled releases of methane fr om a stack agreed with the
known emission fluxes to within ± 15%.Reference: QBN1701-TCEQ-2007 Page 46 of 85

Checked by: 

### Measurements of gas cell concentrat ions during the Texas measurement campaign

.

A series of measurements was made of a 10 cm gas cell filled with a pentane standard gas mixture provided by TCEQ/REFINERY. The measur ements were made by placing the gas cell in the output transmitted beam. This introduces an absorption into the DIAL signal at zero range, which has the effect of introducing an o ffset in the signals, e quivalent to the total concentration-pathlength of the gas in the cell. The differential absorption for pentane at the wavelengths used for the VOC DIAL measuremen ts was determined from the NPL quantified spectral database, and this was used to calculate the concentration of pentane in the gas cell. In addition a number of other gas cell measurem ents were made of propane and benzene.

The results of these measurements are given in Table A1.3 below. These present the means of a
series of measurements made of the gas cells on different days.

Date Scans Cell Measured
column Concentration (ppm)

Predicted Actual
27/07/2007 110-112 10 cm propane 0.57 ± 0.04 8180 ± 530 8413

27/07/2007 117-123 10 cm pentane 1.16 ± 0.12 7100 ± 700 7500

30/07/2007 222-223 10cm pentane 1.34 ± 0.20 8200 ± 1200 7500

07/08/2007 371-372 10cm pentane 1.24 ± 0.01 7600 ± 100 7500

17/08/2007 557-558 20cm benzene 0.09 900 ± 70 1000

Table A1.3, Measurements of gas cell concentrations. The uncertainty figures are base d on the standard deviation of the individual measurements.Reference: QBN1701-TCEQ-2007 Page 47 of 85

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### NPL open-path calibration facility

NPL has also deve loped and operate a full-scale facilit y for the calibration of open path monitors, including DIAL. This consists of a 10 m long window less cell able to maintain a uniform, independently-monitored concentration of a gaseous species al ong its length. This provides a known controlled section of the at mosphere with traceable concentration over a defined range (10m). The absen ce of windows removes reflectio ns and other artefacts from measurements made using optical techniques, prov iding a direct way to validate and assess the
calibration of DIAL instruments.

The calibration facility is windowless with a 1 m diameter, to minimise any beam reflections
from the cell walls and ends. At each end of the cell is an annular calibra tion-gas feed ring with multiple outlets injecting the cal ibration gas mixture into the ce ll. A ring of tangential fans around the centre of the cell extract gas and entrai ned air pulled in through the open ends of the
cell. This ensures the backscatter in the cell approximates to the ambient air conditions. Each fan has a long exhaust tube to avoid r ecirculation of the gas into the cell.

This facility has been employed to directly validate VOC measurements by the NPL DIAL facility [2].

Figure A1.1 The NPL 10m calibration cell.

The facility provides the ability to generate a defined concentration path and so it also provides range-resolution validation for DIAL and lidar instruments. The system was used to validate
the DIAL with a number of measurements of prop ane and methane, as a part of its acceptance tests for Siemens, Shell and British Gas.

[1] Measurements of the Emissions to At mosphere of Volatile Organic Compounds from the Hellenic Aspropyrgos Oil Refinery; T D Gardiner, M.J.T. Milton, R.A. Robinson, P.T.Woods, A.S.Andrews, H. D’Souza, D Alfonso, N.R Swann; NPL Report QM S99, Sept 1996

[2] Calibration of DIAL and Open Path Systems Using Extern al Gas Cells; M.J.T. Milton, P.T. Woods, R.H. Partridge, B.A G oody; Proc. Europto, Munich 1995.Reference: QBN1701-TCEQ-2007 Page 48 of 85

Checked by: 

## Annex 2 Speciated VOC measur ements and Flux Correction
Factors

The DIAL measures VOCs by measuring the diffe rential absorption of two wavelengths of light. The wavelengths used, at around 3000 cm-1, ar e chosen to measure, in effect, the C-H stretch in the hydrocarbons for C3 and above. The sensitivity of the DIAL is slightly different to different hydro carbons, and for example an oxygenated hydrocarbon will give a different absorption per mass than a straight chain alkane. The differential absorption strength used was calibrated to give a mass emission rate for a gasoline vapour. A different ‘cocktail’ of hydrocarbons would give a slig htly different response per unit mass. Air samples were taken at locations which would pr ovide an indication of the actual speciation of the emission fluxes sampled by the DIAL. If the actual (relative) composition is known, from the air sample analyses, then by determin ing the absorption of each constituent it is possible to determine a correction factor which will provide the true ‘mass value’ assuming the emissions measured have a similar relative composition to the sampled air.



### Flux Correction Factors

The multi-component analysis of the ambient air sample results was used to determine the differential absorption coefficient (in m 2 g-1) for the particular co cktail of hydrocarbons in each sample. This was done by taking the differential absorption coefficient for each species from the NPL quantified database of the infr ared absorption of industrial organic species, and scaling it by the mass-fraction of that sp ecies in the sample. The standard DIAL differential absorption coefficient for VOC measurements is 0.49 m2g-1, based on the infrared absorption of gasoline vapour.

These results are summarised in Table A2.1 , which show the differential absorption coefficients, and the factor by which the st andard DIAL VOC flux results need to be multiplied by to take into account the particular VOC mix present.Reference: QBN1701-TCEQ-2007 Page 49 of 85

Checked by: Table A2.1. Flux correction factors determ ined from each of the air samples.

Air samples were taken at a number of locati ons around the plants. Figures A2.1, A2.2, A2.3 and A2.4 show the locations of the sample s. The Air samples were taken using SUMO canisters and pumped Perkin Elmer Auto matic Thermal Desorption (ATD) tubes.

The ATD tubes were sampled at a flow rate of 40ml/min, to enable a comparison between the SUMO canisters and the ATD tubes; a flow restrictor was fitted to canister, so each sample was taken over the same time period.

The sampler tubes are approximately 6mm OD and length 90mm long. The sampler tubes contained approximately 200milligrams to 300 m illigrams of sorbent. Two sorbent tubes were used in series containing two sorbent materials used, a porous polymer (Tenax TA) and a carbon black (Carbopack X). Different so rbents are needed to cover the diverse boiling point ranges and chemical functional groups of VOCs.

The SUMO canister analysis gave resu lts in the Carbon number range of C 2 -C 10 , whilst the linked ATD tubes containing Te nax TA and Carbopack-X gave a Carbon number range of
C 4 -C 22 Tube Sample diff abs flux factor

DTTS1 0.62 0.8
DTTS2 0.39 1.3
DTTS3 0.55 0.9
DTTS4 0.31 1.6
DTTS5 0.29 1.7
DTTS6 0.41 1.2
DTTS7 0.37 1.3
DTTS8 0.41 1.2
DTTS9 0.44 1.1
DTTS10 0.46 1.1
DTTS11 0.24 2.0
DTTS12 0.43 1.1
DTTS13 0.24 2.1
DTTS14 0.50 1.0
DTTS15 0.44 1.1

DTTS16 0.47 1.0Reference: QBN1701-TCEQ-2007 Page 50 of 85

Checked by: Figure A2.1 Location of air samples around the naphtha tanks at the Bulk TerminalReference: QBN1701-TCEQ-2007 Page 51 of 85

Checked by: Figure A2.2 Location of air samples in th e crude oil storage areas at the Refinery.

Figure A2.3 Location of air samples in the ga soline tanks and coker areas at the Refinery. DTTS 5

DTTS 6 DTTS 7 DTTS 11

DTTS 8 DTTS 12

DTTS 9 & 10 DTTS 16Reference: QBN1701-TCEQ-2007 Page 52 of 85

Checked by: Figure A2.4 Location of air samples in the ga soline tanks and coker areas at the Refinery. DTTS 13 DTTS DTTS 15Reference: QBN1701-TCEQ-2007 Page 53 of 85

Checked by: 

### Sampling Procedure

The ATD tubes were attached to the flow restrict or so as the tubes were at the same height as the top of flow restrictors sample entry point.

The samples were taken at a height of appr oximately 2m by mounting the sampling array on a Tripod. The samples were taken by opening the valve on the SUMO canister and starting the sampling pumps. The flow restrictors had b een set so as they sampled over a period of
1.25 hours. ATD Tubes

Flow restrictorReference: QBN1701-TCEQ-2007 Page 54 of 85

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### Analysis of the ATD tubes

The method of analysis was based on EN IS O 16017-2 [1] and was carried out using UKAS (United Kingdom Accreditation Service) accredited method QPDQM/B/526. This method combines Automatic Thermal Desorption w ith Gas Chromatography, with a Flame Ionisation Detector [1]

The analysis instrument used is an Automated Thermal Desorb er autosampler coupled to a Gas Chromatograph usually with a flame ionisa tion detector. The VOCs are released from the sampler tube using a heated oven in an inert gas stream of helium. The VOCs are refocused onto a small cold trap prior to tr ansfer onto the gas chromatography column. Generally a coated fused silica gas chromat ography column of diameter 320 micrometers and length 60 meters is used to separate the individual VOCs collected. Using VOC standard materials, the identification of the individual VOC components are compared to the column elution time (retention time) of the standard VOC materials. The mass of VOCs collected is quantified using the flame ionisation detector. A series of calibrations standards
are used to calibrate the flame ionisation det ector response. The concentration of the VOC in ambient air is then calculated using fr om the mass collected and the volume of air sampled.

Tables A2.2 and A2.3 present the results from the canister and tube analyses respectively. The tube analyses were carried out by NPL’s in house accredit ed analysis laboratory, the canister samples were analysed by EAS Environm ental Analytical Service, Inc, California.Reference: QBN1701-TCEQ-2007 Page 55 of 85

Checked by: Table A2.2 Full results of the speciation analyses on the Canister Samples. Sample No. DTTS1 DTTS2 DTTS3 DTTS4 DTTS5 DTTS6 DTTS7 DTTS8 Date 17-Jul07 18-Jul07 19-Jul07 21-Jul07 28-Jul07 28-Jul07 29-Jul07 30-Jul07 Start time 17:17 16:20 12:31 03:57 14:25 14:40 16:56 16:39 End time 18:09 17:27 13:44 05:06 15:47 16:00 18:12 17:51 Average Wind Direction/deg 164 128 322 95 170 174 149 159 Average Wind Speed/mph 4.5 2.4 4.6 2.3 4.3 4.3 3.9 4.2 Cannister Number 169 610 708 881 190 996 762 606

Species ppb V ppb V ppb V ppb V ppb V ppb V ppb V ppb V Ethene <1.93 <1.91 4.76 <1. 91 <1.96 <1.94 <2.00 20.24 Acetylene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 Ethane <1.93 1.98 15.93 3. 14 2.83 10.86 7.01 223.95 Propene <1.93 <1.91 <2.09 <1. 91 <1.96 <1.94 <2.00 <2.06 Propane <1.93 6.32 10.65 2. 15 <1.96 5.45 12.16 23.61 I-Butane 3.73 5.17 12.74 8.22 6.02 16.72 8.00 72.47 Methanol <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 1-Butene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 1,3-Butadiene <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 4.88 n-Butane <1.93 <1.91 24. 44 2.43 <1.96 3.97 6.69 11.16 t-2-Butene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 4.70 c-2-Butene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 Ethanol <1.93 <1.91 <2.09 7. 52 <1.96 <1.94 <2.00 2402.7 3-Methyl-1-butene <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 Acetone <1.93 <1.91 <2.09 <1. 91 <1.96 <1.94 <2.00 <2.06 i-Pentane 323.89 5.67 63.51 17.78 4.80 26.94 8.13 36.51 1-Pentene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 Isopropanol <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 2-Methyl-1-butene <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 n-Pentane <1.93 <1.91 38.65 <1.91 <1.96 2.65 2.35 39.77 Isoprene <1.93 <1.91 <2.09 <1. 91 <1.96 <1.94 <2.00 <2.06 t-2-Pentene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 c-2-Pentene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 Tert butyl alcohol <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Methyl-2-butene <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 2,2-Dimethylbutane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 Cyclopentene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 n-Propanol <1.93 <1.91 2.78 <1.91 <1.96 <1.94 <2.00 4.66 Cyclopentane <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 Methyl tert butyl ether <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 2,3-Dimethylbutane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Methylpentane <1.93 <1.91 8.13 <1.91 <1.96 <1.94 <2.00 <2.06 3-Methylpentane <1.93 <1.91 5.33 <1.91 <1.96 <1.94 <2.00 <2.06 1-Hexene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 n-Hexane <1.93 <1.91 10.26 <1 .91 <1.96 <1.94 <2.00 12.04 Diisopropyl ether <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 3-Methylcyclopentene <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 <2.00 <2.06 Ethyl tert butyl ether <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 Methylcyclopentane <1.93 <1.91 3.77 <1.91 <1.96 <1.94 <2.00 <2.06 2,4-Dimethylpentane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 Benzene <1.93 <1.91 3.17 <1 .91 <1.96 <1.94 5.19 <2.06 Cyclohexane <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Methylhexane <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 2,3-Dimethylpentane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 3-Methylhexane <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Methyl-1-hexene <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06Reference: QBN1701-TCEQ-2007 Page 56 of 85

Checked by: Sample No. DTTS1 DTTS2 DTTS3 DTTS4 DTTS5 DTTS6 DTTS7 DTTS8 Date 17-Jul07 18-Jul07 19-Jul07 21-Jul07 28-Jul07 28-Jul07 29-Jul07 30-Jul07 Start time 17:17 16:20 12:31 03:57 14:25 14:40 16:56 16:39 End time 18:09 17:27 13:44 05:06 15:47 16:00 18:12 17:51 Average Wind Direction/deg 164 128 322 95 170 174 149 159 Average Wind Speed/mph 4.5 2.4 4.6 2.3 4.3 4.3 3.9 4.2 Cannister Number 169 610 708 881 190 996 762 606

Tert amyl methyl ether <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 2,2,4-Trimethylpentane <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 <2.00 <2.06 n-Heptane <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 Methylcyclohexane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 2,5-Dimethylhexane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 2,4-Dimethylhexane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 2,3,4-Trimethylpentane <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 <2.00 <2.06 Toluene <1.93 <1.91 3.03 <1.91 1.99 <1.94 3.35 28.65 2,3-Dimethylhexane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Methylheptane <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 4-Methylheptane <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Ethyl-3-methylpentane <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 <2.00 <2.06 3-Methylheptane <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Methyl-1-heptane <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 n-Octane <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 2.12 Ethylbenzene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 m,p-xylene <1.93 2.74 <2.09 <1 .91 <1.96 <1.94 <2.00 2.84 Styrene <1.93 <1.91 <2.09 <1. 91 <1.96 <1.94 <2.00 <2.06 o-xylene <1.93 <1.91 <2.09 <1. 91 <1.96 <1.94 <2.00 <2.06 1-Nonene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 n-Nonane <1.93 4.09 <2.09 <1. 91 <1.96 <1.94 <2.00 <2.06 i-Propylbenzerne <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 n-Propylbenzerne <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 a-Pinene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 3-Ethyltoluene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 4-Ethyltoluene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 1,3,5-Trimethylbenzene <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 <2.00 <2.06 2-Ethyltoluene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 b-Pinene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 1,2,4-Trimethylbenzene <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 2.07 <2.06 n-Decane <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 1,2,3-Trimethylbenzene <1.93 <1.91 <2 .09 <1.91 <1.96 <1.94 <2.00 2.28 Indan <1.93 <1.91 <2.09 <1. 91 <1.96 <1.94 <2.00 <2.06 d-Limonene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 1,3-Diethylbenzene <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 1,4-Diethylbenzene <1.93 <1.91 <2. 09 <1.91 <1.96 <1.94 <2.00 <2.06 n-Butylbenzene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 1,4-Dimethyl-2-ethylbenzene <1.93 <1. 91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 1,3-Dimethyl-4-ethylbenzene <1.93 <1. 91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 1,2-Dimethyl-4-ethylbenzene <1.93 <1. 91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 Undecane <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 1,2,4,5-Tetramethylbenzene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 1,2,3,5-Tetramethylbenzene <1.93 <1.91 <2.09 <1.91 <1.96 <1.94 <2.00 <2.06 Napthalene <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06 Dodecane <1.93 <1.91 <2.09 <1 .91 <1.96 <1.94 <2.00 <2.06Reference: QBN1701-TCEQ-2007 Page 57 of 85

Checked by: Sample No. DTTS9 DTTS10 DTTS11 DTTS12 DTTS13 DTTS14 DTTS15 DTTS16 Date 3-Aug07 3-Aug07 5-Aug07 6-Aug07 7-Aug07 17-Aug07 17-Aug07 18-Aug07 Start time 13:30 15:37 04:48 04:30 04:55 17:53 17:29 20:05 End time 14:47 17:28 06:03 05:54 06:19 18:58 18:30 20:57 Average Wind Direction/deg 84 113 183 140 201 131 131 128 Average Wind Speed/mph 4.3 5 3.4 2.6 2 4.4 4.7 2.4 Cannister Number 2968 711 782 2962 2970 758 732 656

Species ppb V ppb V ppb V ppb V ppb V ppb V ppb V ppb V Ethene 9.65 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 Acetylene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 Ethane 24.58 27.98 5.36 117. 36 3.35 9.17 6.96 15.92 Propene <1.94 <1.97 <1.94 <1. 96 <1.93 <2.00 <1.88 <2.00 Propane 28.92 14.99 8.47 48. 25 80.36 13.33 16.46 10.30 I-Butane 15.23 9.19 7.12 39.59 5.26 20.06 15.94 5.97 Methanol <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 1-Butene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 1,3-Butadiene <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 3.09 <2.00 n-Butane 16.33 9.88 4.99 64.73 <1.93 11.47 29.96 5.95 t-2-Butene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 c-2-Butene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 Ethanol <1.94 <1.97 <1.94 <1. 96 <1.93 <2.00 <1.88 <2.00 3-Methyl-1-butene <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 Acetone <1.94 <1.97 <1.94 <1. 96 <1.93 <2.00 <1.88 <2.00 i-Pentane 19.88 <1.97 <1. 94 <1.96 8.87 53.05 110.80 16.86 1-Pentene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 Isopropanol <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 2-Methyl-1-butene <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 n-Pentane <1.94 <1.97 <1. 94 <1.96 <1.93 4.64 39.57 11.68 Isoprene <1.94 <1.97 <1.94 <1. 96 <1.93 <2.00 <1.88 <2.00 t-2-Pentene <1.94 <1.97 <1.94 2.85 <1.93 <2.00 <1.88 <2.00 c-2-Pentene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 Tert butyl alcohol <1.94 <1.97 <1 .94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Methyl-2-butene <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 2,2-Dimethylbutane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 5.39 <2.00 Cyclopentene <1.94 2.91 <1.94 9.48 <1.93 <2.00 <1.88 <2.00 n-Propanol <1.94 2.11 <1.94 2.86 <1.93 <2.00 <1.88 <2.00 Cyclopentane <1.94 <1.97 <1.94 <1.96 <1.93 2.25 <1.88 <2.00 Methyl tert butyl ether <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 2,3-Dimethylbutane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Methylpentane <1.94 <1.97 <1. 94 <1.96 <1.93 5.21 <1.88 10.70 3-Methylpentane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 5.76 1-Hexene 2.88 <1.97 <1.94 <1. 96 <1.93 <2.00 <1.88 <2.00 n-Hexane <1.94 <1.97 <1.94 <1 .96 6.72 <2.00 <1.88 <2.00 Diisopropyl ether <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 3-Methylcyclopentene <1.94 <1.97 <1 .94 <1.96 <1.93 <2.00 <1.88 <2.00 Ethyl tert butyl ether <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 Methylcyclopentane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 2,4-Dimethylpentane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 Benzene <1.94 <1.97 <1.94 <1 .96 4.58 <2.00 <1.88 <2.00 Cyclohexane <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Methylhexane <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 2,3-Dimethylpentane <1.94 <1.97 <1 .94 <1.96 <1.93 <2.00 <1.88 7.20 3-Methylhexane <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Methyl-1-hexene <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00Reference: QBN1701-TCEQ-2007 Page 58 of 85

Checked by: Sample No. DTTS9 DTTS10 DTTS11 DTTS12 DTTS13 DTTS14 DTTS15 DTTS16 Date 3-Aug07 3-Aug07 5-Aug07 6-Aug07 7-Aug07 17-Aug07 17-Aug07 18-Aug07 Start time 13:30 15:37 04:48 04:30 04:55 17:53 17:29 20:05 End time 14:47 17:28 06:03 05:54 06:19 18:58 18:30 20:57 Average Wind Direction/deg 84 113 183 140 201 131 131 128 Average Wind Speed/mph 4.3 5 3.4 2.6 2 4.4 4.7 2.4 Cannister Number 2968 711 782 2962 2970 758 732 656

Tert amyl methyl ether <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 2,2,4-Trimethylpentane <1.94 <1.97 <1 .94 <1.96 <1.93 <2.00 <1.88 <2.00 n-Heptane <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 5.54 <2.00 Methylcyclohexane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 2,5-Dimethylhexane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 2,4-Dimethylhexane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 2,3,4-Trimethylpentane 3.92 <1.97 2. 58 <1.96 <1.93 <2.00 <1.88 <2.00 Toluene <1.94 <1.97 <1. 94 <1.96 1.96 12.26 20.52 2.11 2,3-Dimethylhexane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Methylheptane <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 4-Methylheptane <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Ethyl-3-methylpentane <1.94 <1.97 <1 .94 <1.96 <1.93 <2.00 <1.88 <2.00 3-Methylheptane <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Methyl-1-heptane <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 n-Octane <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 2.09 <2.00 Ethylbenzene <1.94 <1.97 <1. 94 <1.96 <1.93 2.04 2.46 <2.00 m,p-xylene <1.94 <1.97 <1.94 <1.96 <1.93 5.51 8.49 <2.00 Styrene <1.94 <1.97 <1.94 <1. 96 <1.93 <2.00 <1.88 <2.00 o-xylene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 2.59 <2.00 1-Nonene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 n-Nonane <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 i-Propylbenzerne <1.94 2.13 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 n-Propylbenzerne <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 a-Pinene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 3-Ethyltoluene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 4-Ethyltoluene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 1,3,5-Trimethylbenzene <1.94 <1.97 <1 .94 <1.96 <1.93 <2.00 <1.88 <2.00 2-Ethyltoluene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 b-Pinene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 1,2,4-Trimethylbenzene <1.94 <1.97 <1 .94 <1.96 <1.93 <2.00 2.06 <2.00 n-Decane <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 1,2,3-Trimethylbenzene 2.54 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 Indan <1.94 <1.97 <1.94 <1. 96 <1.93 <2.00 <1.88 <2.00 d-Limonene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 1,3-Diethylbenzene <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 1,4-Diethylbenzene <1.94 <1.97 <1. 94 <1.96 <1.93 <2.00 <1.88 <2.00 n-Butylbenzene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 1,4-Dimethyl-2-ethylbenzene <1.94 <1. 97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 1,3-Dimethyl-4-ethylbenzene <1.94 <1. 97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 1,2-Dimethyl-4-ethylbenzene <1.94 <1. 97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 Undecane <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 1,2,4,5-Tetramethylbenzene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 1,2,3,5-Tetramethylbenzene <1.94 <1.97 <1.94 <1.96 <1.93 <2.00 <1.88 <2.00 Napthalene <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00 Dodecane <1.94 <1.97 <1.94 <1 .96 <1.93 <2.00 <1.88 <2.00Reference: QBN1701-TCEQ-2007 Page 59 of 85

Checked by: Table A2.3 Full results of the speciation analyses on the Sorbent Tube Samples.

Sample No. TRV BLK A TRV BLK B DTTS1 DTTS2 DTTS3 DTTS4 DTTS5

Date 17-Jul-07 18-Jul-07 19-Jul-07 21-Jul-07 28-Jul-07
Start time 17:17 16:20 12:31 03:57 14:25
End time 18:09 17:27 13:44 05:06 15:47 Sample Volume/ml 2500.5 3230.8 2970.4 3297.5 3948.6 Average Wind Direction/deg 164 128 322 95 170 Average Wind Speed/mph 4.5 2.4 4.6 2.3 4.3 ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v
i-Butane 0.8 0.7 4.4 1.6 13.1 7.5 2.4
n-Butane <0.6 <0.6 <0.6 0.6 19.3 1.0 <0.6
trans-2-Butene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
1-Butene <0.6 <0.6 <0.6 <0.6 0.8 <0.6 <0.6 2-methylpropene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
cis-2-butene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,3 Butadiene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 i-pentane <0.6 <0.6 60.8 0.9 13.7 1.9 0.6 1-pentene <0.6 <0.6 2.8 <0.6 0.9 <0.6 <0.6
2 me-1-butene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 isoprene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-pentane <0.6 <0.6 <0.6 1.4 34.6 1.1 <0.6 cis-2-pentene (Z)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 trans-2-pentene (E)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2 dime cyclopropane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,2-di me butane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cyclo pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-me-1-pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,3-di me butane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cyclo pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2-me pentane <0.6 <0.6 <0.6 <0.6 7.1 <0.6 <0.6 4-me-cis-2-pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-me-trans-2-pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 3-me pentane <0.6 <0.6 <0.6 <0.6 3.6 <0.6 <0.6
1-hexene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-hexane <0.6 <0.6 6.5 <0.6 11.8 <0.6 <0.6 cis-2-hexene (Z)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
trans-3-hexene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 trans-2-hexene (E)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 methylcyclopentane <0.6 <0.6 <0.6 <0.6 3.0 <0.6 <0.6 2,4 di me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,2,3-trimethyl-1-butene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,2,3-tri-me butane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
benzene <0.2 <0.2 0.2 0.2 5.0 1.8 0.2 cyclohexane <0.6 <0.6 <0.6 <0.6 1.5 <0.6 <0.6 2-methyl hexane <0.6 <0.6 <0.6 <0.6 1.2 <0.6 <0.6 2,3 di me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
3-me hexane <0.6 <0.6 <0.6 <0.6 1.6 <0.6 <0.6 cyclohexene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1-heptene <0.6 <0.6 <0.6 <0.6 0.9 <0.6 <0.6 2,2,4 tri me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-heptane <0.6 <0.6 <0.6 <0.6 2.3 <0.6 <0.6 methylcyclohexane <0.6 <0.6 <0.6 <0.6 2.0 <0.6 <0.6 2,3,4 tri me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,3,3-tri me pentane <0.6 <0.6 <0.6 <0.6 2.7 2.4 <0.6Reference: QBN1701-TCEQ-2007 Page 60 of 85

Checked by: Sample No. TRV BLK A TRV BLK B DTTS1 DTTS2 DTTS3 DTTS4 DTTS5

Date 17-Jul-07 18-Jul-07 19-Jul-07 21-Jul-07 28-Jul-07
Start time 17:17 16:20 12:31 03:57 14:25
End time 18:09 17:27 13:44 05:06 15:47 Sample Volume/ml 2500.5 3230.8 2970.4 3297.5 3948.6 Average Wind Direction/deg 164 128 322 95 170 Average Wind Speed/mph 4.5 2.4 4.6 2.3 4.3 ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v
toluene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2-methyl heptane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-methyl heptane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cycloheptene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cycloheptane <0.6 <0.6 <0.6 <0.6 1.0 <0.6 <0.6
n-octane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 ethylbenzene <0.6 <0.6 <0.6 <0.6 1.5 <0.6 <0.6 m/p-xylene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
2 me octane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
3 me octane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 styrene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 o-xylene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
nonane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cis-cyclooctene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 isopropylbenzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cyclooctane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-propylbenzene <0.6 <0.6 <0.6 <0.6 <0.6 1.0 <0.6 3-ethyl toluene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-ethyl toluene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,3,5 tri me benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2-ethyl toluene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
2-me nonene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2,4 tri me benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-decane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2,3-Trimethylbenzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2,3,5-tetra me benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-butyl benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-undecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-pentylbenzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-dodecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 naphthalene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-tridecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-tetradecane <0.6 <0.6 <0 .6 <0.6 <0.6 <0.6 <0.6 n-pentadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-hexadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-heptadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-octadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-nonadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-cosane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-docosane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6Reference: QBN1701-TCEQ-2007 Page 61 of 85

Checked by: Sample No. DTTS6 DTTS7 DTTS8 DTTS9 DTTS10 DTTS11 DTTS12
Date 28-Jul-07 29-Jul-07 30-Jul-07 3-Aug-07 3-Aug-07 5-Aug-07 6-Aug-07
Start time 14:40 16:56 16:39 13:30 15:37 04:48 04:30
End time 16:00 18:12 17:51 14:47 17:28 06:03 05:54 Sample Volume/ml 3927.9 3637.8 3409.8 5289 3600.9 3980.4 Average Wind Direction/deg 174 149 159 84 113 183 140 Average Wind Speed/mph 4.3 3.9 4.2 4.3 5 3.4 2.6 ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v
i-Butane 7.5 9.6 24.8 6.5 9.4 3.2 11.8
n-Butane 8.7 4.2 9.8 <0.6 13.8 3.4 21.6
trans-2-Butene <0.6 <0.6 1.3 <0.6 <0.6 <0.6 1.1
1-Butene <0.6 <0.6 1.4 <0.6 <0.6 <0.6 1.0 2-methylpropene <0.6 <0.6 1.4 <0.6 <0.6 <0.6 0.9
cis-2-butene <0.6 <0.6 1.0 <0.6 <0.6 <0.6 <0.6 1,3 Butadiene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 i-pentane 5.4 2.6 16.5 0.7 7.3 2.2 21.4 1-pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
2 me-1-butene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 isoprene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-pentane 3.6 1.5 1.6 <0.6 6.4 0.8 4.0 cis-2-pentene (Z)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 trans-2-pentene (E)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2 dime cyclopropane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,2-di me butane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cyclo pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-me-1-pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,3-di me butane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cyclo pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2-me pentane 0.7 <0.6 <0.6 <0.6 0.8 <0.6 1.7 4-me-cis-2-pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-me-trans-2-pentene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 3-me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1.0
1-hexene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-hexane 0.9 <0.6 <0.6 <0.6 1.7 <0.6 1.9 cis-2-hexene (Z)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
trans-3-hexene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 trans-2-hexene (E)- <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 methylcyclopentane 0.6 <0.6 <0.6 <0.6 0.7 <0.6 1.1 2,4 di me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,2,3-trimethyl-1-butene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2,2,3-tri-me butane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
benzene 0.9 4.4 0.5 0.2 0.7 0.3 1.6 cyclohexane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2-methyl hexane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 0.7 2,3 di me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
3-me hexane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 0.7 cyclohexene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1-heptene <0.6 <0.6 0.9 <0.6 <0.6 <0.6 1.1 2,2,4 tri me pentane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-heptane <0.6 <0.6 <0.6 <0.6 0.9 <0.6 <0.6 methylcyclohexane 0.6 4.8 <0.6 <0.6 0.8 <0.6 0.8 2,3,4 tri me pentane <0.6 1.7 <0.6 <0.6 <0.6 <0.6 <0.6 2,3,3-tri me pentane 1.6 0. 9 1.4 <0.6 0.8 1.5 2.1Reference: QBN1701-TCEQ-2007 Page 62 of 85

Checked by: Sample No. DTTS6 DTTS7 DTTS8 DTTS9 DTTS10 DTTS11 DTTS12
Date 28-Jul-07 29-Jul-07 30-Jul-07 3-Aug-07 3-Aug-07 5-Aug-07 6-Aug-07
Start time 14:40 16:56 16:39 13:30 15:37 04:48 04:30
End time 16:00 18:12 17:51 14:47 17:28 06:03 05:54 Sample Volume/ml 3927.9 3637.8 3409.8 5289 3600.9 3980.4 Average Wind Direction/deg 174 149 159 84 113 183 140 Average Wind Speed/mph 4.3 3.9 4.2 4.3 5 3.4 2.6 ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v ppb v/v
toluene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2-methyl heptane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-methyl heptane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cycloheptene <0.6 <0.6 <0.6 <0.6 <0.6 10.0 <0.6 cycloheptane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-octane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 ethylbenzene <0.6 <0.6 1.5 <0.6 <0.6 <0.6 1.4 m/p-xylene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
2 me octane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
3 me octane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 styrene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 o-xylene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
nonane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cis-cyclooctene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 isopropylbenzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 cyclooctane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-propylbenzene 0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 3-ethyl toluene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 4-ethyl toluene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,3,5 tri me benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 2-ethyl toluene <0.6 <0.6 <0.6 <0.6 <0.6 1.3 <0.6
2-me nonene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2,4 tri me benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-decane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2,3-Trimethylbenzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 1,2,3,5-tetra me benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-butyl benzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-undecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-pentylbenzene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-dodecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 naphthalene <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-tridecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-tetradecane <0.6 <0.6 <0 .6 <0.6 <0.6 <0.6 <0.6 n-pentadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-hexadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 n-heptadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-octadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-nonadecane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-cosane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6
n-docosane <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6Reference: QBN1701-TCEQ-2007 Page 63 of 85

Checked by: Sample No. DTTS13 DTTS14 DTTS15 DTTS16
Date 7-Aug-07 17-Aug07 17-Aug07 18-Aug07 Start time 04:55 17:53 17:29 20:05
End time 06:19 18:58 18:30 20:57 Sample Volume/ml 4000.8 3217.6 2833.9 2532.6 Average Wind Direction/deg 201 131 131 128 Average Wind Speed/mph 2 4.4 4.7 2.4 ppb v/v ppb v/v ppb v/v ppb v/v
i-Butane 2.1 10.7 4.0 4.0
n-Butane 0.6 22.8 9.0 7.3
trans-2-Butene <0.6 5.2 2.7 <0.6
1-Butene <0.6 1.6 1.0 <0.6 2-methylpropene <0.6 1.5 0.6 <0.6
cis-2-butene <0.6 3.7 1.9 <0.6 1,3 Butadiene <0.6 <0.6 <0.6 <0.6 i-pentane 1.0 82.2 37.6 8.1 1-pentene 1.1 0.8 0.6 <0.6
2 me-1-butene <0.6 <0.6 <0.6 <0.6 isoprene <0.6 7.7 2.8 4.2 n-pentane <0.6 23.7 8.2 4.2 cis-2-pentene (Z)- <0.6 3.1 1.3 <0.6 trans-2-pentene (E)- <0.6 <0.6 <0.6 <0.6 1,2 dime cyclopropane <0.6 3.8 1.5 <0.6 2,2-di me butane <0.6 <0.6 <0.6 <0.6 cyclo pentene <0.6 <0.6 <0.6 <0.6 4-me-1-pentene <0.6 <0.6 <0.6 <0.6 2,3-di me butane <0.6 2.0 0.7 <0.6 cyclo pentane <0.6 <0.6 <0.6 <0.6 2-me pentane 2.7 11.4 4.2 1.6 4-me-cis-2-pentene <0.6 <0.6 <0.6 <0.6 4-me-trans-2-pentene 0.8 <0.6 <0.6 <0.6 3-me pentane <0.6 6.1 2.4 0.8
1-hexene <0.6 <0.6 <0.6 <0.6
n-hexane 5.3 13.0 4.0 1.6 cis-2-hexene (Z)- <0.6 <0.6 <0.6 <0.6
trans-3-hexene <0.6 0.6 <0.6 <0.6 trans-2-hexene (E)- <0.6 <0.6 <0.6 <0.6 methylcyclopentane <0.6 7.5 2.0 <0.6 2,4 di me pentane <0.6 <0.6 <0.6 <0.6 2,2,3-trimethyl-1-butene <0.6 <0.6 <0.6 <0.6 2,2,3-tri-me butane <0.6 <0.6 <0.6 <0.6
benzene 5.1 12.9 6.7 1.3 cyclohexane <0.6 4.0 2.0 1.5 2-methyl hexane <0.6 3.8 1.3 <0.6 2,3 di me pentane <0.6 0.7 <0.6 <0.6
3-me hexane 0.7 4.1 1.6 <0.6 cyclohexene <0.6 <0.6 <0.6 <0.6 1-heptene <0.6 1.3 <0.6 <0.6 2,2,4 tri me pentane <0.6 <0.6 <0.6 <0.6 n-heptane <0.6 5.7 1.6 <0.6 methylcyclohexane 0.6 6.6 1.7 0.6 2,3,4 tri me pentane <0.6 <0.6 <0.6 <0.6 2,3,3-tri me pentane 0.7 15.2 7.9 <0.6Reference: QBN1701-TCEQ-2007 Page 64 of 85

Checked by: Sample No. DTTS13 DTTS14 DTTS15 DTTS16
Date 7-Aug-07 17-Aug07 17-Aug07 18-Aug07 Start time 04:55 17:53 17:29 20:05
End time 06:19 18:58 18:30 20:57 Sample Volume/ml 4000.8 3217.6 2833.9 2532.6 Average Wind Direction/deg 201 131 131 128 Average Wind Speed/mph 2 4.4 4.7 2.4 ppb v/v ppb v/v ppb v/v ppb v/v
toluene <0.6 <0.6 <0.6 <0.6 2-methyl heptane <0.6 <0.6 <0.6 <0.6 4-methyl heptane <0.6 1.3 <0.6 <0.6 cycloheptene <0.6 3.3 <0.6 <0.6 cycloheptane <0.6 <0.6 0.9 <0.6
n-octane <0.6 2.2 1.8 <0.6 ethylbenzene 0.9 9.4 5.3 <0.6 m/p-xylene <0.6 <0.6 <0.6 <0.6
2 me octane <0.6 0.6 <0.6 <0.6
3 me octane <0.6 <0.6 <0.6 <0.6 styrene <0.6 3.1 1.5 <0.6 o-xylene <0.6 1.6 <0.6 <0.6
nonane <0.6 <0.6 <0.6 <0.6 cis-cyclooctene <0.6 <0.6 <0.6 <0.6 isopropylbenzene <0.6 <0.6 <0.6 <0.6 cyclooctane <0.6 <0.6 <0.6 <0.6 n-propylbenzene <0.6 0.6 <0.6 0.6 3-ethyl toluene <0.6 <0.6 <0.6 <0.6 4-ethyl toluene <0.6 0.7 <0.6 <0.6 1,3,5 tri me benzene <0.6 <0.6 <0.6 <0.6 2-ethyl toluene <0.6 0.6 <0.6 <0.6
2-me nonene <0.6 1.3 <0.6 <0.6 1,2,4 tri me benzene <0.6 0.9 <0.6 <0.6
n-decane <0.6 0.7 <0.6 <0.6 1,2,3-Trimethylbenzene <0.6 <0.6 <0.6 <0.6 1,2,3,5-tetra me benzene <0.6 <0.6 <0.6 <0.6 n-butyl benzene <0.6 0.8 <0.6 <0.6
n-undecane <0.6 <0.6 <0.6 <0.6 n-pentylbenzene <0.6 <0.6 <0.6 <0.6
n-dodecane <0.6 <0.6 <0.6 <0.6 naphthalene <0.6 <0.6 <0.6 <0.6
n-tridecane <0.6 <0.6 0.6 <0.6
n-tetradecane <0.6 <0.6 0.6 <0.6 n-pentadecane <0.6 <0.6 <0.6 <0.6
n-hexadecane <0.6 <0.6 <0.6 <0.6 n-heptadecane <0.6 <0.6 <0.6 <0.6
n-octadecane <0.6 <0.6 <0.6 <0.6
n-nonadecane <0.6 <0.6 <0.6 <0.6
n-cosane <0.6 <0.6 <0.6 <0.6
n-docosane <0.6 <0.6 <0.6 <0.6Reference: QBN1701-TCEQ-2007 Page 65 of 85

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## Annex 3. Meteorological Measurements

Wind direction and speed were recorded dur ing the DIAL measurements at one fixed location, at the north east of the Bulk Termin al site, and using a ma st located on the DIAL facility itself. Two further me teorological stations were ope rated by TCEQ, located to the
north and south of the REFINERY site (one of these stations was located at the southern side of Bulk Terminal during the period measurements were being made at Bulk Terminal). The NPL fixed mast provided wind speed and di rection at two heights, ~ 3m and 11m. In general the fixed mast data have been used to derive the wind fiel d for the DIAL flux measurements, though in some cases the DIAL wind has been used where it was observed to be more representative of local conditions.

The following series of plots present the wind roses, taken from the 11m wind vane mounted on the fixed meteorological mast.

Figure 3.1 Wind rose diagram – top mast – 16 July 2007Reference: QBN1701-TCEQ-2007 Page 66 of 85

Checked by: Figure 3.2 Wind rose diagram – top mast – 17 July 2007Reference: QBN1701-TCEQ-2007 Page 67 of 85

Checked by: Figure 3.3 Wind rose diagram – top mast – 18 July 2007Reference: QBN1701-TCEQ-2007 Page 68 of 85

Checked by: Figure 3.4 Wind rose diagram – top mast – 19 July 2007Reference: QBN1701-TCEQ-2007 Page 69 of 85

Checked by: Figure 3.5 Wind rose diagram – top mast – 20 & 21 July 2007Reference: QBN1701-TCEQ-2007 Page 70 of 85

Checked by: Figure 3.6 Wind rose diagram – top mast – 28 July 2007Reference: QBN1701-TCEQ-2007 Page 71 of 85

Checked by: Figure 3.7 Wind rose diagram – top mast – 29 July 2007Reference: QBN1701-TCEQ-2007 Page 72 of 85

Checked by: Figure 3.8 Wind rose diagram – top mast – 30 July 2007Reference: QBN1701-TCEQ-2007 Page 73 of 85

Checked by: Figure 3.9 Wind rose diagram – top mast – 31 July 2007Reference: QBN1701-TCEQ-2007 Page 74 of 85

Checked by: Figure 3.10 Wind rose diagram – top mast – 1 August 2007Reference: QBN1701-TCEQ-2007 Page 75 of 85

Checked by: Figure 3.11 Wind rose diagram – top mast – 2 August 2007Reference: QBN1701-TCEQ-2007 Page 76 of 85

Checked by: Figure 3.12 Wind rose diagram – top mast – 3 August 2007Reference: QBN1701-TCEQ-2007 Page 77 of 85

Checked by: Figure 3.13 Wind rose diagram – top mast – 5 & 6 August 2007Reference: QBN1701-TCEQ-2007 Page 78 of 85

Checked by: Figure 3.14 Wind rose diagram – top mast – 6 & 7 August 2007Reference: QBN1701-TCEQ-2007 Page 79 of 85

Checked by: Figure 3.15 Wind rose diagram – top mast – 7 & 8 August 2007Reference: QBN1701-TCEQ-2007 Page 80 of 85

Checked by: Figure 3.16 Wind rose diagram – top mast – 9 August 2007Reference: QBN1701-TCEQ-2007 Page 81 of 85

Checked by: Figure 3.17 Wind rose diagram – top mast – 10 August 2007Reference: QBN1701-TCEQ-2007 Page 82 of 85

Checked by: Figure 3.18 Wind rose diagram – top mast – 11 August 2007Reference: QBN1701-TCEQ-2007 Page 83 of 85

Checked by: Figure 3.19 Wind rose diagram – top mast – 14 August 2007Reference: QBN1701-TCEQ-2007 Page 84 of 85

Checked by: Figure 3.20 Wind rose diagram – top mast – 17 August 2007Reference: QBN1701-TCEQ-2007 Page 85 of 85

Checked by: Figure 3.21 Wind rose diagram – top mast – 18 August 2007