Ozone Exceedances Assessment Department of Environmental Quality

5 Parish Baton Rouge Area

Exceedances Occurred on:8/8/02 9/11/02

4/27/03 7/18/03 8/18/03

Analysis Presented September 16, 2003By: Hall Bohlinger, Robert Hannah, James Hazlett,

Manop Vanichchagorn & Jennifer Walton

Agenda

Welcome Concern over Ozone Exceedances Ozone Exceedance Assessment

– Monitored Data– Back Wind Trajectories– Actual Emissions

Recent Actions Next Steps

1-hour exceedances occurred at the following monitors in 2002:

1-hour Max, ppb(125 ppb)

8/8/02 9/11/02

LSU 102 154

Capitol 131 164

Port Allen 128 102

Bayou Plaquemine 66 139

1-hour exceedances occurred at the following monitors in 2003:

1-hour Max, ppb(125 ppb)

4/27/03 7/18/03 8/18/03

LSU 88 174 108

Capitol 78 147 139

Port Allen 81 129 144

Carville 129 129 74

2001 2002 2003

E. Baton Rouge Baker 0 YES

Capitol 2 2 1.3 NOLSU 1 1 0.7 YESPride 0 YES

Iberville Bayou Plaquemine 1 1 0.7 YESCarville 2 0.7 YESGrosse Tete 0 YES

W. Baton Rouge Port Allen 1 2 1 YES

Ascension Dutchtown 0 YES

Livingston French Settlement 0 YES

# of exce. days for 5 parish area 1 2 3

Ozone 1-HRBaton Rouge Five-Parish Area

average number of

excee. daysattainment CITY

number of exceedance days per yearPARISH

Exceedance Notice – as of 9/15/03

1-hr Exceedances / Design Values

Baton Rouge Area

20

14

11

98

9

11

13 13

15

9

45

4

11

4

8

6

2

11

12

3

18

179 179

169165

161157

144

164 164168 168

149

132 135139

134139

133126

135128

135131

163

154150

140134 135 134

144 142148

137

127121 118

123 121 124 123 124

111

193

120128

121

137

0

5

10

15

20

25

30

35

80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03

Nu

mb

er o

f E

xcee

dan

ce D

ays

40

60

80

100

120

140

160

180

Des

ign

Val

ue,

pp

b

Days Highest Design Value Total Sites Average Design Value

Baton Rouge Area

32

6

3

1

3 3

10

1

3 3

1

3

10 0

1 10

10

10

4

7 7

5

2 21

2

01

4

1

82 83 84 8477 78 77 78 75 77

82 80

0

2

4

6

8

10

12

14

# ex

ceed

ance

day

s

0

10

20

30

40

50

60

70

80

90

Des

ign

Val

ue, p

pb

2001 2002 2003 DV

8-hr Exceedances/Design Values

85 ppb standard

Recent ozone events occurred on days predicted to be green or low yellow air quality.

On 8/18/03 the cloud cover was predicted to be about 65%.

Afternoon clouds did not arrive, however, and cloud cover was actually closer to 10%.

Ozone events characterized by low wind speed and temperatures in the 90’s.

Ozone events appear to be very localized and not regional in nature.

While the Baton Rouge Capitol Site is dominated by mobile sources 90% of the time, recent ozone events were preceded by spikes of VOCs not characteristic of mobile sources.

Common Factors During Baton Rouge Ozone Episodes

1-hr

(ppb)

8-hr

(ppb)

AM Forecast 91 70

PM Forecast 91 70

Maximum Measured Value

174 119

Measured values are much higher than predicted values for both 1-hr and 8-hr concentrations.

Ozone Forecast for 7/18/03

Ozone Forecast for 8/18/03

1-hr

(ppb)

8-hr

(ppb)

AM Forecast 88 75

PM Forecast 72 60

Maximum Measured Value

144 112

Measured values are much higher than predicted values for both 1-hr and 8-hr concentrations.

Improving the Understanding of Ozone Episodes

Rate of ozone formation characterization

Identify VOC species which are the most significant contributors to ozone formation

Improve analysis of monitored VOC variability during & preceding episodes

Back trajectory analysis to locate possible sources

Acquire better understanding of plant-to-plant emissions variability during ozone episodes

NO2 + hv NO + O O + O2 O3

NO + O3 NO2 + O2

How is ozone formed?

O3 + hv O2 + O O + H2O 2 OH

OH + O2 + RH RO2 + H2O RO2 + NO RO + NO2

Reactive VOCs interact with hydroxyl radicals to convert NO to NO2

The outcome of these reactions is the additional NO2 formed photolizes producing more ozone – less NO is available to scavenge the ozone

RO + O2 HRHO + HO2 HO2 + NO NO2 + OH

Rate of Ozone Formation:In the hour preceding exceedances

Rate of Ozone Formation (ppb/hr)

0

10

20

30

40

50

60

70

7.18

.03(

BC)

7.18

.03(

LSU)

7.18

.03(

PA)

7.18

.03(

CV)

8.18

.03(

BC)

8.18

.03(

PA)

9.11

.02(

LSU)

9.11

.02(

BC)

9.11

.02(

BP)

pp

b/h

r

RATE (ppb/hr)10-15 ppb/hr = typical > 40 ppb/hr = rapid ozone formation

0

20

40

60

80

100

120

140

160

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

hour

con

cen

trar

tio

n,

pp

b

NO NOX NO2 SO2 Ozone

Capitol Site 7/18/2003

12:00-1:00 = 60 ppb ozone increase

1 hr stnd - 125 ppb

0

20

40

60

80

100

120

140

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

hour

con

cen

trat

ion

, p

pb

NO NOx NO2 SO2 Ozone

Port Allen Site 7/18/2003

11:00-12:00 = 50 ppb ozone increase

9:00-10:00 = 50 ppb ozone increase

1 hr stnd - 125 ppb

Most Abundant VOC Species Identified at BR Capitol Site

(Top 10 Represent 48% of Total VOC)

propanen-butaneethaneisopentane (2-methylbutane )ethyleneisobutane (2-methylpropane)propylenen-pentanetoluenen-hexane

Ranked by abundance in ppbc

The incremental reactivity characterizes the ozone formation potential of a VOC specie and all of its

reaction products.

VOC Specie Maximum Incremental Reactivity (MIR)

methane 0.005 mol Ozone/mol C

propylene 2.750 mol Ozone/mol C

butane 0.310 mol Ozone/mol C

benzene 0.110 mol Ozone/mol C

ethane 0.080 mol Ozone/mol C

propane 0.150 mol Ozone/mol C

isoprene 2.580 mol Ozone/mol C

ethylene 2.160 mol Ozone/mol C

toluene 0.740 mol Ozone/mol C

Isopentane 0.410 mol Ozone/mol C

VOC Species at BR Capitol SiteRanked by Ozone Forming Potential

(Top 10 Represent 95% of Total Reactivity)

ethylenepropyleneisoprenem/p-xylene1-butenen-butaneisopentane (2-methylbutane )tolueneo-xyleneisobutane (2-methylpropane)

Ranked by abundance in ppbc * MIR Red indicates HRVOC species with recently lowered RQ.

Ethylene Air Releases2001 & 2002 TRI

0

50000

100000

150000

200000

250000

300000

350000

400000

450000B

AS

F

Cro

mpto

n

Geis

mar

Vin

yls

Shell

Chem

ical

Vulc

an

Will

iam

s O

lefins

Deltech

Exxon P

oly

ole

fins

Exxon P

lastics

Exxon R

efinery

Exxon C

hem

ical

Form

osa P

lastics

Cosm

ar

GA

Gulf

Dow

DS

M C

opoly

mer

Pla

cid

Refinin

g

Po

un

ds

2001 2002 Ascension

Iberville

West BTREast BTR

Ethylene Air Releases - Reported in TRI

0

500000

1000000

1500000

2000000

2500000

Po

un

ds

WBR 41440 31000 40250

Iberville 544241 420008 324938

EBR 632798 542697 581747

Ascension 866769 705447 636988

2000 2001 2002

VOC Diurnal Profiles

Typical Diurnal Profiles

0

50

100

150

200

250

Hour

TN

MH

C

Capitol Pride Bayou Plaquemine

Typically VOC concentrations peak during 6-9am period and reach lowest levels during late afternoon hours.

The ozone event on 7/18/2003 was preceded by above normal spikes of VOCs.

Capitol Site TNMHC7/17-18/2003

0

200

400600

800

1000

1200

0 3 6 9 12

15

18

21 0 3 6 9 12

15

18

21

Hour

TN

MH

C p

pb

c

7/17-18/03 Annual Average

Capitol Site

3:00 pm exceedance

147ppb

0

50

100

150

200

250

300

350

400

450

500

hour

co

ncen

trati

on

, p

pb

VOC, ppbc Ozone

Note the peaks in VOC concentration throughout the ozone exceedance.

The ozone event on 8/18/2003 was also preceded by above normal spikes of VOCs.

Capitol Site TNMHC8/17-18/2003

0

500

1000

1500

0 3 6 9 12

15

18

21 0 3 6 9 12

15

18

21

Hour

TH

MH

C p

pb

c

8/17-18/03 Annual Average

Capitol Site

2:00 pm exceedance

139 ppb

Analysis of VOC Profiles

The Hydrocarbon Profile (fingerprint) of Capitol Site is usually very consistent and dominated by mobile source emissions, particularly during the morning rush hour (6-9am).

An analysis of peak concentrations observed before & during ozone events has indicated sources of VOC’s other than mobile.

The Capitol site 6-9am sample on 8/17/03 showed impact of source very similar to evaporative gasoline.

A sample collected just 3 hours later shows entirely different source domination in the VOC profile. Profile dominated by very light VOCs including the highly reactive species, ethylene & propylene.

Capitol Site Sample 8/17/03

0

5

10

15

20

25

% T

NM

HC

Mobile 9am-12pm 8/17/2003

Normal mobile-dominated source profile versus profile of sample containing above normal amounts of HRVOC’s

Isobutane

Ethylene Propane

Propylene

Southern University Site detects frequent hits of industrial emissions.

Continuous VOC monitor triggers canister collection during periods of above normal VOC concentrations.

Sampler has triggered 43 times so far during 2003.

Multiple VOC profiles have been observed.

Total VOC concentrations up to nearly 7 ppm have been observed with hits of MTBE hits up to 400 ppbv.

Concentrations of highly reactive VOCs, ethylene & propylene, commonly observed in the 30 – 60 ppbc range.

Southern Event 7/17/0311pm

0

5

10

15

20

25

% T

NM

HC

Mobile SU 7/17

The night before the July 18th ozone event, the Southern monitor was triggered by a source contributing ethylene & isobutane.

Isobutane

Ethylene

Were these samples impacted from the same source ?

0

5

10

15

20

25

% T

NM

HC

Capitol 8/17/03 9am to noon Southern U 7/17 11pm

The capitol site sample preceding 8/18/03 ozone event & Southern spike sample preceding 7/18/03 ozone event appear to have been impacted by the same source emitting primarily ethylene & isobutane.

Isobutane

Ethylene

Southern University Spike8/23/03 - 4am

0

50

100

150

200

250

Ethylen

e

Acetyl

ene

Ethane

Propyle

ne

Propan

e

Isobut

ane

1-bute

ne

1,3-but

adien

e

n-buta

ne

t2-b

utene

c2-b

utene

2-meth

ylbutan

e

1-pen

tene

n-pen

tane

isopr

ene

t2-p

enten

e

c2-p

enten

e

2,2-dim

ethylbu

tane

cyclo

pentan

e

2,3-dim

ethylbu

tane

2-meth

ylpentan

e

3-meth

ylpentan

e

1-hex

ene

n-hex

ane

meth

ylcyclo

pentan

e

2,4-dim

ethylpe

ntan

e

benze

ne

cyclo

hexan

e

2-meth

ylhexan

e

2,3-dim

ethylpe

ntan

e

3-meth

ylhexan

e

2,2,4-tri

methylp

entan

e

n-hep

tane

meth

ylcyclo

hexan

e

2,3,4-tri

methylp

entan

eto

luene

2-meth

ylheptan

e

3-meth

ylheptan

e

n-octa

ne

ethylb

enze

ne

m/p

xylen

e

styren

e

o xylene

n-non

ane

cum

ene

n-pro

pylbe

nzene

m-et

hyltolue

ne

p-ethylt

oluene

1,3,5-tri

methylb

enze

ne

o-ethylt

oluene

1,2,4-tri

methylb

enze

ne

n-dec

ane

1,2,3-tri

methylb

enze

ne

m-d

iethy

lbenze

ne

p-diet

hylbe

nzene

n-und

ecan

e

pp

bc

Pro

pan

eIsobutane

Eth

ylen

e

Pro

pyl

ene

Southern Event Monitor Spikes

0

25

5075

100

125

150

0 45 90 135 180 225 270 315 360

Wind Direction

pp

bc

Propylene Ethylene

An analysis of the wind direction when ethylene/propylene spikes occur indicates two local sources – one source to the north-northeast of the site and a second source to the northwest of the site.

South Scotlandville Event Monitor Spikes

0

25

5075

100

125

150

0 45 90 135 180 225 270 315 360

Wind Direction

pp

bc

Propylene Ethylene

The south Scotlandville event monitor is triggered less often but indicates a source to the south with another possible source north to northeast of the site.

BTR Ozone History & Progress

In Nov. 1990, BTR was designated as a serious ozone non-attainment area. The attainment date was set for Nov. 1999.

The first Ozone Task Force was formed. Rate of Progress commitments were made to reduce

VOC emissions - 15% by 1994; 9% by 1996 Despite progress in reducing emissions and the number

of exceedance days, BTR failed to meet the Nov. 1999 attainment date.

The second Ozone Task Force convened. Effective June 23, 2003, the BTR area was bumped up

to a severe ozone non-attainment classification.

Approx tons: 1990 = 39,000 2002 = 13,000

67% Reduction

5 Parish Baton Rouge Area Point Source VOC Emissions

0

10000

20000

30000

40000

500001

99

0

19

93

19

94

19

95

19

96

19

97

19

98

19

99

20

00

20

01

20

02

To

ns

Approx tons: 1990 = 66,700 2002 = 42,300

37% Reduction

0

20000

40000

60000

800001

99

0

19

93

19

94

19

95

19

96

19

97

19

98

19

99

20

00

20

01

20

02

To

ns

5 Parish Baton Rouge Area Point Source NOx Emissions

Consequences of the Exceedances:Continued Non-Attainment

No chance for attainment with the 1 hour standard for 2003 or 2004

Attainment date is 2005 Severe non-attainment designation remains

– RFG– Offsets – increased to 1.3 to 1– Redefinition of Major Source – lowered to 25 tpy– Penalty Fees?

Consequences of Continued Non-Attainment & Severe Status: Penalty Fees

CAA Section 185 requires the assessment of penalty fees on facilities in an area designated as severe if the area fails to reach attainment by 2005.

Fees are assessed for each ton of NOx and VOC emissions in excess of 80% of the source’s baseline amount.

Fee is equal to $5000 per ton plus an annual CPI adjustment; predicted to be $7500 per ton.

Based on actual 2002 emissions, annual fees for some local companies will likely equal (in millions):

– Dow - $14.8 Shell Chem. - $1.9 PCS - $2– Exxon Chem. - $6.3 Exxon Ref. - $7.9 Placid - $1.8

Recent Actions

Emergency rule to lower HRVOC RQs– Effective 8/12/03– 18 of 20 notices received as a result of emergency rule

Administrative Order – 9/3/03– Maintain and submit HRVOC data by 10/3/03

Additional monitoring– Speciated VOC event monitors added at Capitol, Port Allen,

LSU and Carville

Discussions with EPA on collaborative effort to study BTR’s ozone exceedances

Next Steps

Permanent rule to lower HRVOC RQs Required speciation of HRVOCs in permits

– Ethylene, propylene & butenes Debate with EPA over Interprecursor Trading Form Ozone Technical Committee - Convene by October

– Evaluate additional data collected (Monitors, RQ’s & AO)– Design studies and determine needed resources by 12/03– Oversee contracted research projects to begin by 5/1/04 and be

complete by 11/04– Recommend control strategies, if needed

Form Ozone Steering Committee -Convene by October– Secure funding for research

For more information…

James Hazlett– 225-219-3554

Manop Vanichchagorn– 225-219-3489

Jennifer Walton– 225-219-3486

LDEQ Ozone Website– http://www.deq.state.la.us/evaluation/ozone/index.htm