SolarSolar OccultationOccultation FluxFluxSolar Solar OccultationOccultation Flux Flux measurementsmeasurements of of NMVOCsNMVOCs

Johan MellqvistJohan Mellqvist

DepDep of Earth and Space Sciencesof Earth and Space SciencesCh l U i i f T h lCh l U i i f T h lChalmers University of Technology,Chalmers University of Technology,

Göteborg,SwedenGöteborg,Sweden,,johan.mellqvist@chalmers.sejohan.mellqvist@chalmers.se

OpticalOptical remoteremote sensingsensing groupgroupOpticalOptical remoteremote sensingsensing groupgroup

Industrial emissions: Measurementswith SOF and tracer correlation of with SOF and tracer correlation of NMVOCs, methane, SO2, NOx, NH3.Areas: refineries, petrochemistry natural

d ti t /d tgas production, upstream/downstream

Ship emissions: Airborne measurementsof SO2, NOx, CO2, particle number and size. Emission factors (g/fuel) and total emissions (g/ )(g/s)

Volcanic emissions: DOAS-network at 21 volcanoes for SO2 (NOVAC), Bo Galle

22

Comparison between NOVAC and GEIA, SO2 emissions from volcanoes (Arellano Chalmers)SO2 emissions from volcanoes (Arellano Chalmers)

NOVACNOVAC

GEIA

kg/s

Typical areas in a refinery from which Typical areas in a refinery from which diffuse leakages of volatile organicdiffuse leakages of volatile organicdiffuse leakages of volatile organic diffuse leakages of volatile organic

compounds (VOC)compounds (VOC) occuroccurp ( )p ( )45

1: Crude oil

3 2: Water treatment

3: Process area

4: Product tanks

5: Product loading

1 2 6. Flaring

Alkanes, 70-80%Aromatic VOC, 10-20%Alkenes 1-5%

Standard Standard methodmethod for the determination for the determination ff f itif iti i i fi i f VOCVOC ffof of fugitivefugitive emissions of emissions of VOCsVOCs from from

industryindustryyy

Storage tanks: Empirical calculation based g pon formulas derived by the US EPA and API(AP 42)

i d k d i bProcess industry: Leak detection by sniffer+API correlationW t t t t fl i hi d Water treatment areas, flaring, ship and truck loading: emission factors by US EPA

55

Why measure diffuse VOCsWhy measure diffuse VOCsyyThe standard approach with calculationsmeans that the industrial site is treatedmeans that the industrial site is treatedas an ideal industry. Leaks are hence not accounted for. accounted for.

Measurements with different techniques(Solar Occultation Flux (SOF) Differential (Solar Occultation Flux (SOF), Differential Absorption LIDAR (DIAL), Airborne, Tracercorrelation) often shows largecorrelation) often shows largediscrepancies compared to estimates.

The Solar The Solar OccultationOccultation Flux Flux methodmethod (SOF) and (SOF) and mobile DOASmobile DOASmobile DOASmobile DOAS 1) The number of

various molecules abovethe vehicle are estimatedthe vehicle are estimatedfrom spectroscopicanalysis of direct solar IR light (SOF) and zenithlight (SOF) and zenithscattered UV light (mobile DOAS) .

2) The measurementsare conducted whiledriving and hence is itdriving and hence is it possible to measure the total mass of moleculesalong the roads traveledalong the roads traveled.

3) The total mass is multiplied by the windmultiplied by the windwhich yields the flux in kg/s.

77Solar tracker

Experience with SOF

Regular surveillance of Swedish refineries since 7 years (60 surveys) It provides the basis for national VOC reporting

p

surveys). It provides the basis for national VOC reporting. Total refinery measurements down to the level of individualleaks are conducted .

Participation in several international campaigns, such as Mexico city 2004, Texas 2006/2009/2011/2012, France 2008 the Netherlands 2008/2010, Antwerpen 2010

In general the measurements show 400-900% larger VOC emissions than reported.

Th t i t f th SOF t i 20 30% Thi The uncertainty of the SOF measurements is 20-30%. This uncertainty is derived from error estimations, validation exercises and instrument comparisons. (The wind uncertainty is the largest error source)uncertainty is the largest error source)

88

99

1010

Fenceline measurements are typically conducted at 0.5 to 3 km distanceFenceline measurements are typically conducted at 0.5 to 3 km distancefrom the sources 100-600 s. The assumption is then that the plume isdistributed from the ground up to several hundred meters height andthat the wind varies little with height.g(This has been validated by airborne measurements during TexAQS2006 [Mellqvist, JGR 2009]). 1111

JM23

Slide 11

JM23 main assumptaion during the campaignJohan Mellqvist, 2007-12-09

SOF SOF measurementsmeasurements of of olefinesolefines and alkanes from and alkanes from petrochemicalpetrochemical conglomerateconglomerate, Mt Belvieu Texas 2009, Mt Belvieu Texas 2009

C2H4

C2H4:453 kg/h

C3H6: 229 kg/h

C3H8: 1615 kg/h

1212

Fi 1 SOF lk h l t f M t B l i f I 10 S i Rd 5 J

Ethene emissions from Mt Belvieu, Houston, measured Ethene emissions from Mt Belvieu, Houston, measured during Texas 2006 by SOF and airborne measurements byduring Texas 2006 by SOF and airborne measurements byduring Texas 2006 by SOF and airborne measurements by during Texas 2006 by SOF and airborne measurements by

NOAA (Joost de NOAA (Joost de GouwGouw, EST 2009) , EST 2009)

Ethene Houston ship channel 2006

F ld h d T it 2009

Alkanes Rotterdam 2008

Formaldehyde Texas city 2009

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SOF versus inventory for recent studiesSOF versus inventory for recent studies Source region Species SOF (kg/h) 2006/2009/2011 Inventory

(k /h)(kg/h)

Houston ship channel2006/2009/2011

EthenePropene

804/ 580/ 612624/ 1653/563

74 772006/2009/2011

(Texas, USA)PropeneAlkanesSO2NO2

624/ 1653/56311528/ 10134/ 11569NA/ 3364/ 2328NA/ NA/ 1829

7785119671297NO2 NA/ NA/ 1829 1297

Total Rotterdam 2008/2010( )

Alkanes 5553 1265(The Netherlands)

Total Le Havre 2008 Alkanes 4407 1048(France)Antwerpen(Belgium)

AlkanesSO2

55102116

7152500(Belgium) SO2

NO221161234

25001167 1515

SomeSome responsesresponses by modellers by modellers and and authoritiesauthorities

TCEQ (Texas Commission on Environmental Quality) TCEQ (Texas Commission on Environmental Quality) increases industrial VOCs by ~6X in ozone increases industrial VOCs by ~6X in ozone modellingmodelling(SIP d l)(SIP d l)(SIP model)(SIP model)Scientists at NOAA (Kim ACP, 2011) have Scientists at NOAA (Kim ACP, 2011) have upscaledupscaled VOC emissions VOC emissions basedbased on SOF 2006 data on SOF 2006 data upscaledupscaled VOC emissions VOC emissions basedbased on SOF 2006 data on SOF 2006 data in Texas. This in Texas. This improvedimproved the the agreementagreement with with airborneairborne measurementsmeasurements. . airborneairborne measurementsmeasurements. . EPA has EPA has admittedadmitted that the API that the API modelmodel is is underpredictingunderpredicting VOC emissions. VOC emissions. TheyThey claimclaim to be to be p gp g yyworkingworking to to improveimprove the emission the emission factorsfactors

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OzoneOzone modellingmodelling for the for the TexAQSTexAQS 2006 2006 campaigncampaign by by usingusingupscaledupscaled VOC and NOx emissionsVOC and NOx emissions basedbased on SOF andon SOF andupscaledupscaled VOC and NOx emissions VOC and NOx emissions basedbased on SOF and on SOF and

comparisoncomparison to to airborneairborne measurementsmeasurements (Kim et al, ACP 2011) (Kim et al, ACP 2011)

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