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Analyzing “Spikiness” in Diurnal Ozone Patterns in Houston
A Case Study Using Region 12 Data to Relate Industrial Emissions to Ambient Air Quality
Dave Sullivan OCE/MO and John Jolly OEPPA/TAD
Why is this important? Because figuring out what causes high O3 in Houston can save $100’s of
millions & protect public health.
In most other areas in Texas, ozone levels typically increase at a fairly predictable,
moderate rate
On high ozone days in Dallas, ozone rises at a steady rate of 15-25 ppb / hr
On high ozone days in Houston, ozone often rises suddenly 50 – 100+ ppb / hr. We believe this comes from the highly chemically reactive air in industrial areas
Given a complete set of monitoring data…
Upset reports, 5 minute resolution
ozone, wind speed, wind direction data,
Hourly auto-GC & other PAMS VOC data,
Area-wide data,
Then we may be better able to police air quality
5-Minute Ozone Readings for CAMS 35 (Deer Park)
9/20/99
0
50
100
150
200
250
9/20/9
9 0:00
9/20/9
9 1:00
9/20/9
9 2:00
9/20/9
9 3:00
9/20/9
9 4:00
9/20/9
9 5:00
9/20/9
9 6:00
9/20/9
9 7:00
9/20/9
9 8:00
9/20/9
9 9:00
9/20/9
9 10:0
09/2
0/99 1
1:00
9/20/9
9 12:0
09/2
0/99 1
3:00
9/20/9
9 14:0
09/2
0/99 1
5:00
9/20/9
9 16:0
09/2
0/99 1
7:00
9/20/9
9 18:0
09/2
0/99 1
9:00
9/20/9
9 20:0
09/2
0/99 2
1:00
9/20/9
9 22:0
09/2
0/99 2
3:00
9/21/9
9 0:00
Date/Time
Ozon
e (pp
b)
Exceptionally steep rise inozone – about 140 ppb in30 minutes
1,3-butadiene upsetdiscovered at 8am
Using “Delta-max” to measure steepness of ozone increase/decrease for a monitor
for a day
1) Delta-max equals greatest hourly increase in ozone concentration
2) Delta-min is greatest hourly decrease following delta-max
3) High values for these two variables indicate possibility of upset emissions, and need to be investigated
4) Charts of delta-max vs delta-min plotted for 5-year period, 1995-99, for all area monitors
with >= 100 ppb hourly ozone
Delta-max and Delta-min at Deer Park CAMS 35 (industrial/urban monitor) 1995-
1999
High Delta-max values show spikiness of ozone concentrations in Houston Ship Channel area
Delta-max and Delta-min at Northwest Harris CAMS 26 (rural/suburban downwind monitor),
1995-1999
Note absence of high values – i.e. less spikiness
Comparing Delta Max in Houston and Dallas
Dallas emissions largely mobile and area sources – much less “spikiness”
Next two slides show distribution of delta-max values in Houston and Dallas over same 5-year period all area monitors >= 100 ppb hourly ozone included
note that Houston’s mean delta-max (34.9 ppb) is above 90th percentile in Dallas
Case Study: 9/20/99
Severe early morning ozone spike at Deer Park C35 monitor
Ozone traveled downwind; spike subsequently recorded at 3 downwind monitors
1,3-butadiene spill reported in morning at a Dynegy plant located on north side of channel, some 6-8 miles NW of the Deer Park monitor
Amount reported was small (50 gals) but estimates of upset releases are notoriously inexact -- plus this is a highly reactive VOC
Map, forward trajectory, and diurnal ozone graphs follow
Map of Affected Area -- Ozone spike detected first at Deer Park, then subsequently at Texas City, Galveston, and Clute, respectively. Winds were from NW, shifting to NE later.
HYSPLIT 24-Hour Forward Trajectory for 9/20/99 Using Upper Air Data
13z (7am cst) start time
Red: 10m starting height
Blue: 100m starting height
Green: 500m starting height
filled icons (near shore): noon cst
outlined icons: 6pm cst
This trajectory starts near Ship Channel, shows initial NW wind flow, followed by NE shift
Local Wind DirectionUsing CAMS
(Deer Park met equipment not functioning; 2 adjacent monitors’ wind data shown)
9/20/99 Wind Direction at Monitors near Deer Park
0
90
180
270
360
6:00
7:00
8:00
9:00
10:0
0
11:0
0
12:0
0
13:0
0
14:0
0
15:0
0
16:0
0
17:0
0
Start Hour (cst)
Com
pass
Deg
rees
Houston East C1
Clinton
5-Minute Ozone Readings for CAMS 35 (Deer Park)
9/20/99
0
50
100
150
200
250
9/2
0/9
9 0
:00
9/2
0/9
9 1
:00
9/2
0/9
9 2
:00
9/2
0/9
9 3
:00
9/2
0/9
9 4
:00
9/2
0/9
9 5
:00
9/2
0/9
9 6
:00
9/2
0/9
9 7
:00
9/2
0/9
9 8
:00
9/2
0/9
9 9
:00
9/2
0/9
9 1
0:0
0
9/2
0/9
9 1
1:0
0
9/2
0/9
9 1
2:0
0
9/2
0/9
9 1
3:0
0
9/2
0/9
9 1
4:0
0
9/2
0/9
9 1
5:0
0
9/2
0/9
9 1
6:0
0
9/2
0/9
9 1
7:0
0
9/2
0/9
9 1
8:0
0
9/2
0/9
9 1
9:0
0
9/2
0/9
9 2
0:0
0
9/2
0/9
9 2
1:0
0
9/2
0/9
9 2
2:0
0
9/2
0/9
9 2
3:0
0
9/2
1/9
9 0
:00
Date/Time
Ozo
ne
(p
pb
)
Exceptionally steep rise inozone – about 140 ppb in30 minutes
1,3-butadiene upsetdiscovered at 8am
5-Minute Ozone Readings for CAMS 10 (Texas City)
9/20/99
0
50
100
150
200
250
9/2
0/9
9 0
:00
9/2
0/9
9 1
:00
9/2
0/9
9 2
:00
9/2
0/9
9 3
:00
9/2
0/9
9 4
:00
9/2
0/9
9 5
:00
9/2
0/9
9 6
:00
9/2
0/9
9 7
:00
9/2
0/9
9 8
:00
9/2
0/9
9 9
:00
9/2
0/9
9 1
0:0
0
9/2
0/9
9 1
1:0
0
9/2
0/9
9 1
2:0
0
9/2
0/9
9 1
3:0
0
9/2
0/9
9 1
4:0
0
9/2
0/9
9 1
5:0
0
9/2
0/9
9 1
6:0
0
9/2
0/9
9 1
7:0
0
9/2
0/9
9 1
8:0
0
9/2
0/9
9 1
9:0
0
9/2
0/9
9 2
0:0
0
9/2
0/9
9 2
1:0
0
9/2
0/9
9 2
2:0
0
9/2
0/9
9 2
3:0
0
9/2
1/9
9 0
:00
Date/Time
Oz
on
e (
pp
b)
Spike occurs about 1.5 - 2hours after Texas City
5-Minute Ozone Readings for CAMS 34 (Galveston)
9/20/99
0
50
100
150
200
250
9/2
0/9
9 0
:00
9/2
0/9
9 1
:00
9/2
0/9
9 2
:00
9/2
0/9
9 3
:00
9/2
0/9
9 4
:00
9/2
0/9
9 5
:00
9/2
0/9
9 6
:00
9/2
0/9
9 7
:00
9/2
0/9
9 8
:00
9/2
0/9
9 9
:00
9/2
0/9
9 1
0:0
0
9/2
0/9
9 1
1:0
0
9/2
0/9
9 1
2:0
0
9/2
0/9
9 1
3:0
0
9/2
0/9
9 1
4:0
0
9/2
0/9
9 1
5:0
0
9/2
0/9
9 1
6:0
0
9/2
0/9
9 1
7:0
0
9/2
0/9
9 1
8:0
0
9/2
0/9
9 1
9:0
0
9/2
0/9
9 2
0:0
0
9/2
0/9
9 2
1:0
0
9/2
0/9
9 2
2:0
0
9/2
0/9
9 2
3:0
0
9/2
1/9
9 0
:00
Date/Time
Oz
on
e (
pp
b)
Spike registered herejust minutes after TexasCity
5-Minute Ozone Readings for CAMS 11 (Clute)
9/20/99
0
50
100
150
200
250
9/2
0/9
9 0
:00
9/2
0/9
9 1
:00
9/2
0/9
9 2
:00
9/2
0/9
9 3
:00
9/2
0/9
9 4
:00
9/2
0/9
9 5
:00
9/2
0/9
9 6
:00
9/2
0/9
9 7
:00
9/2
0/9
9 8
:00
9/2
0/9
9 9
:00
9/2
0/9
9 1
0:0
0
9/2
0/9
9 1
1:0
0
9/2
0/9
9 1
2:0
0
9/2
0/9
9 1
3:0
0
9/2
0/9
9 1
4:0
0
9/2
0/9
9 1
5:0
0
9/2
0/9
9 1
6:0
0
9/2
0/9
9 1
7:0
0
9/2
0/9
9 1
8:0
0
9/2
0/9
9 1
9:0
0
9/2
0/9
9 2
0:0
0
9/2
0/9
9 2
1:0
0
9/2
0/9
9 2
2:0
0
9/2
0/9
9 2
3:0
0
9/2
1/9
9 0
:00
Date/Time
Ozo
ne (
pp
b)
4 hours later, spike registers fardownwind at Clute monitor
Name Description MWt MIR [d]2M-2-BUT 2-Methyl-2-Butene 70.14 14.45T3M2-C5E Trans 3-Methyl-2-Hexene 84.16 14.171M-CC5E 1-Methyl cyclopentene 82.15 13.95T-2-BUTE trans-2-Butene 56.11 13.9113-BUTDE 1,3-Butadiene 54.09 13.58C3M2-C5E Cis-3-Methyl-2-Hexene 84.16 13.3823M2-BUT 2,3-Dimethyl-2-Butene 84.16 13.32C-2-BUTE cis-2-Butene 56.11 13.222M-2-C5E 2-Methyl-2-Pentene 84.16 12.28PROPENE Propene 42.08 11.58ISOPRENE Isoprene 68.12 10.6923M2-C5E 2,3-Dimethyl-2-Hexene 98.19 10.411-BUTENE 1-Butene 56.11 10.29C-2-PENT cis-2-Pentene 70.14 10.24T-2-PENT trans-2-Pentene 70.14 10.232-C5-OLE 2-Pentenes 70.14 10.23ETHENE Ethene 28.05 9.08C6-OL2D C6 Cyclic or di-olefins 82.15 8.65C-2-C6E Cis-2-Hexene 84.16 8.44T-2-C6E Trans-2-Hexene 84.16 8.442-C6-OLE 2-Hexenes 84.16 8.44C-3-C6E Cis-3-Hexene 84.16 8.22T-3-C6E Trans-3-Hexene 84.16 8.16T4M2-C5E Trans 4-Methyl-2-Hexene 84.16 7.881M-CC6E 1-Methyl Cyclohexene 96.17 7.811-PENTEN 1-Pentene 70.14 7.79CYC-PNDE Cyclopentadiene 66.1 7.61C7-OL2D C7 Cyclic or di-olefins 96.18 7.49CYC-PNTE Cyclopentene 68.12 7.38T-2-C7E Trans-2-Heptene 98.19 7.333M-1-BUT 3-Methyl-1-Butene 70.14 6.99
Reactivity of 1,3-Butadiene compared to selected olefin species
(W. Carter, 5/2000, http://www.cert.ucr.edu/~carter/reactdat.htm)
Next: Looking at 1,3-butadiene at Deer Park
Deer Park Auto-GC measures 1,3-butadiene, but was not functioning on 9/20/99, hampering this investigation
Looked at data for this chemical at Deer Park in 1999 overall, instead
Following charts show wind directions, by frequency, of high 1,3-butadiene measurements
In 1999, very high measurements most frequently came from NNW -- same direction as 9/20/99
High 1,3-Butadiene Measurements by Wind Direction at Deer Park
0
1
2
3
4
Number of measurements >= 20 ppb in 1999(n=15; 1999 mean = 1.006)
N
E
S
W
Very
Summary O3 spikes in Houston from industrial emissions
From upset emissions or regular releases of reactive species
Results of summer 2000 & 2001 studies shed light on this
Auto-GC data at Deer Park on study date would have been useful in identifying 1,3 butadiene.
Without auto-GC data, FO spent time checking company records to find link between spill & ozone
Bottom line: MonOps & TAD need complete auto-GC and CAMS data to do forensic studies for Field Ops