Emissions of Criteria and Toxic Emissions of Criteria and Toxic Pollutants from Portland Cement Pollutants from Portland Cement Manufacturing Plants in SCAQMDManufacturing Plants in SCAQMD

National Association of Clean Air National Association of Clean Air Agencies Meeting Agencies Meeting

August 6, 2008August 6, 2008

Mohsen Nazemi, P.E.Mohsen Nazemi, P.E.Deputy Executive OfficerDeputy Executive Officer

Cement Manufacturing Cement Manufacturing EmissionsEmissions

Existing and Proposed New Existing and Proposed New StandardsStandards•• EPAEPA

•• SCAQMDSCAQMD

SCAQMD’s Chromium Emission SCAQMD’s Chromium Emission StudyStudy

Cement Handling and Production Cement Handling and Production in SCAQMDin SCAQMD

Riverside Cement ProductionRiverside Cement Production•• Gray CementGray Cement

No existing cement kilnsNo existing cement kilnsAverage of 670,894 tons/year (2004Average of 670,894 tons/year (2004--2007)2007)

•• White CementWhite CementTwo white cement kilnsTwo white cement kilnsAverage of 104,551 tons/year (2004Average of 104,551 tons/year (2004--2007)2007)

California Portland Cement ProductionCalifornia Portland Cement Production•• Gray CementGray Cement

Two gray cement kilnsTwo gray cement kilnsAverage of 807,831 tons/year (2004Average of 807,831 tons/year (2004--2007)2007)

Numerous other batch plants and concrete Numerous other batch plants and concrete recyclers in the area recyclers in the area

Applicable RequirementsApplicable Requirements

EPA RequirementsEPA Requirements•• NESHAP (40 CFR 63, Subpart LLL)NESHAP (40 CFR 63, Subpart LLL)•• NSPS (40 CFR 60, Subpart F)NSPS (40 CFR 60, Subpart F)•• NSR/PSD (PM 2.5 & Others)NSR/PSD (PM 2.5 & Others)

SCAQMD RequirementsSCAQMD Requirements•• NSR for Criteria Pollutants (BACT, Offset, and Modeling)NSR for Criteria Pollutants (BACT, Offset, and Modeling)•• NSR for Toxics (1NSR for Toxics (1--10 in10 in--aa--million, Tmillion, T--BACT, Hazard Index BACT, Hazard Index

of 1)of 1)•• Source Specific Rule Source Specific Rule

PM10 Reductions from Cement Manufacturing (Rule 1156)PM10 Reductions from Cement Manufacturing (Rule 1156)•• Other Applicable Rules and RegulationsOther Applicable Rules and Regulations

Opacity (Rule 401)Opacity (Rule 401)Fugitive Dust (Rule 403)Fugitive Dust (Rule 403)

NESHAP Emission StandardsNESHAP Emission Standards

Kilns @ Major SourcesKilns @ Major Sources•• PM PM << 0.3 lb/ton0.3 lb/ton•• Opacity Opacity << 20%20%

Kilns @ Major and Area SourcesKilns @ Major and Area Sources•• Dioxin/Furan Dioxin/Furan << 0.2 0.2 ng/dscmng/dscm (0.4 if inlet < 400 (0.4 if inlet < 400 00F)F)•• THC THC << 50 50 ppmvppmv•• Mercury Mercury << 41 41 ug/dscmug/dscm or use of a scrubberor use of a scrubber

Clinker Coolers and All Others @ Major SourcesClinker Coolers and All Others @ Major Sources•• PM PM << 0.1 lb/ton (clinker coolers only)0.1 lb/ton (clinker coolers only)•• Opacity Opacity << 10%10%

Current NSPS Emission Current NSPS Emission StandardsStandards

KilnsKilns

•• PM PM << 0.3 lb/ton0.3 lb/ton•• Opacity Opacity << 20%20%Clinker CoolersClinker Coolers

•• PM PM << 0.1 lb/ton0.1 lb/ton•• Opacity Opacity << 10%10%All OthersAll Others

•• Opacity Opacity << 10%10%

Proposed NSPS Emission Proposed NSPS Emission StandardsStandards

EPA Proposed NSPS amendment on EPA Proposed NSPS amendment on 5/30/085/30/08Applies to new Kilns and Clinker CoolersApplies to new Kilns and Clinker CoolersProposed Emission StandardsProposed Emission Standards•• PM PM << 0.086 lb/ton0.086 lb/ton•• NOx NOx << 1.50 lb/ton (301.50 lb/ton (30--day rolling average)day rolling average)•• SO2 SO2 << 1.33 lb/ton (301.33 lb/ton (30--day rolling average) or day rolling average) or

90% emission reduction90% emission reduction

Current Rule 1156 RequirementsCurrent Rule 1156 Requirements

Visible EmissionsVisible Emissions•• NonNon--open piles open piles -- << 10% opacity per EPA Method 910% opacity per EPA Method 9•• Open piles Open piles -- << 20% opacity per SCAQMD Method 9B20% opacity per SCAQMD Method 9B•• Visible Dust Plum Visible Dust Plum << 100 ft100 ft

Air Pollution Control DeviceAir Pollution Control Device•• PM PM << 0.01 gr/ft0.01 gr/ft33 (installed prior to 11/4/05)(installed prior to 11/4/05)•• PM PM << 0.005 gr/ft0.005 gr/ft33 (installed after 11/4/05)(installed after 11/4/05)

Open clinker storage is allowed if area is Open clinker storage is allowed if area is << 4 4 acres or loading/unloading rate is acres or loading/unloading rate is << 80,000 80,000 tons/monthtons/monthOpen material storage is allowed if 90% of Open material storage is allowed if 90% of material is larger than ½ inchmaterial is larger than ½ inch

Proposed Rule 1156 Proposed Rule 1156 AmendmentsAmendments

Eliminate enclosure threshold for clinker storageEliminate enclosure threshold for clinker storage•• Thereby requiring total enclosure of all clinker storage and Thereby requiring total enclosure of all clinker storage and

handlinghandling•• Enclosure required by March 1, 2009Enclosure required by March 1, 2009

Modify exemption for nonModify exemption for non--clinker materialsclinker materials•• 90% of materials mass is larger than ½ inch90% of materials mass is larger than ½ inch

Clarifying changesClarifying changes•• Opacity observationsOpacity observations•• Enclosed conveyors & transfer points vented to air pollution Enclosed conveyors & transfer points vented to air pollution

control devicecontrol device

Proposed amendments up for adoption on September 5, Proposed amendments up for adoption on September 5, 20082008

Reported Emissions of Criteria Reported Emissions of Criteria Pollutants from Cement Plants*Pollutants from Cement Plants*

(Tons/Year)(Tons/Year)

California California Portland CementPortland Cement

Riverside Riverside CementCement

VOCVOC 99 11

NOxNOx 794794 6262

SOxSOx 109109 33

COCO 7373 22

TSPTSP 117117 107107

*Based on 2006-07 Annual Emission Report

Reported Emissions of Toxic Reported Emissions of Toxic Pollutants from Cement Plants*Pollutants from Cement Plants*

(Lbs./Year)(Lbs./Year)Pollutant Description Riverside Cement California Portland

1,3-Butadiene 1.573 7.855

Ammonia 302.394 1962.888

Arsenic 1.748 0.371

Benzene 47.279 331.383

Beryllium 0.093 0.051

Cadmium 3.831 48.698

Chromium (VI) 1.281 0.159

Formaldehyde 95.249 16730.79

Lead (inorganic) 11.694 3.306

Naphthalene 0.143 0.084

Nickel 8.554 17.152

PAHs, total, with components not reported 46.668 4.932

*Based on 2006-07 Annual Emission Report

SCAQMD’s Hexavalent SCAQMD’s Hexavalent ChromiumChromium

Emission Study from Emission Study from Cement PlantsCement Plants

What Triggered the Investigation of What Triggered the Investigation of Cr+6 Emissions from Cement Plants?Cr+6 Emissions from Cement Plants?

Analysis of data completed in late Analysis of data completed in late 2007 as part of Multiple Air Toxics 2007 as part of Multiple Air Toxics Exposure Study (MATESExposure Study (MATES--III) showed III) showed high Cr+6 at one air monitoring high Cr+6 at one air monitoring station (Rubidoux in Riverside station (Rubidoux in Riverside County)County)Investigation was conducted to Investigation was conducted to identify the source(s) of Cr+6 identify the source(s) of Cr+6 emissions emissions

Hexavalent Chromium

Hexavalent ChromiumHexavalent ChromiumMATESMATES--IIIIII

0.0

0.1

0.2

0.3

0.4

0.5

0.6

Anaheim Burbank Central LA Compton Fontana HuntingtonPark

North LongBeach

Pico Rivera Rubidoux Wilmington Average RubidouxFilter Blank

ng/m3 MATES II AQMD Lab data MATES III Year 1 MATES III Year 2

Metal Processes22%

Heavy Duty Diesel Trucks

3%

Trains and Marine

1%

Off-Road Equipment

19%On-Road Gasoline

36%

Paved Road Dust19%

2005 Hexavalent Chromium 2005 Hexavalent Chromium Emissions in theEmissions in the

South Coast Air BasinSouth Coast Air Basin

Initial InvestigationInitial Investigation

Permit Records ReviewPermit Records ReviewSurvey of AreaSurvey of AreaLiterature ReviewLiterature ReviewWind Pattern AnalysisWind Pattern AnalysisDeposition Plates DeploymentDeposition Plates Deployment

Initial ActionsInitial Actions

Examined permit records and Examined permit records and surveyed area for potential surveyed area for potential hexavalent chromium sourceshexavalent chromium sourcesNo major hexavalent chromium No major hexavalent chromium sources foundsources foundReports and literature did NOT Reports and literature did NOT indicate that emissions of hexavalent indicate that emissions of hexavalent chromium from cement facilities chromium from cement facilities were significantwere significant

Wind Pattern Analysis at Western Wind Pattern Analysis at Western Riverside Monitoring StationRiverside Monitoring Station

•• Most frequent wind direction is from Most frequent wind direction is from the Westthe West

•• However, higher levels of However, higher levels of hexavalent chromium are measured hexavalent chromium are measured when wind blows from the Northeastwhen wind blows from the Northeast

•• The cement production facilities are The cement production facilities are located over two miles to the located over two miles to the NortheastNortheast

Western Riverside Air Monitoring Station

TXI Riverside Cement

California PortlandCement

prevailing wind

Location of Cement Plants and Monitoring Station

Deposition Plates DeploymentDeposition Plates Deployment

Glass plates placed to collect falling Glass plates placed to collect falling particlesparticlesA good survey tool for covering a wide areaA good survey tool for covering a wide areaNot used for determining true atmospheric Not used for determining true atmospheric concentrationsconcentrationsThree rounds of deployment in the areaThree rounds of deployment in the area•• Jan, Feb, MarJan, Feb, Mar

All three rounds showed higher hexavalent All three rounds showed higher hexavalent chromium content of deposited particles chromium content of deposited particles near Riverside Cementnear Riverside Cement

Cr6 Deposition Plate Results - Round 3Highest MiddleLowest

Cal Portland

TXI Riverside

Distribution of Deposition Plates

1.46

0.70

0.21

0.28

0.31

Hexavalent Chromium Averages (ng/m3)Feb. 12 – May 31, 2008

MATES-III Basin Average = 0.20

MATES-III Rubidoux Average = 0.39

PM samplers for Hexavalent Chromium

0.35

0.20

0.08*

* Less than 10 samples collected to date

Cal Portland

TXI Riverside

Extensive Area Sweep for Other Extensive Area Sweep for Other Hexavalent Chromium SourcesHexavalent Chromium Sources

More than 50 square mile area More than 50 square mile area around Riverside Cementaround Riverside CementIdentified 444 regulated or Identified 444 regulated or potentially regulated sourcespotentially regulated sourcesNone had hexavalent chromium None had hexavalent chromium emissions at levels that would lead emissions at levels that would lead to the observed monitored to the observed monitored concentrationsconcentrations

Emission TestingEmission Testing

White cement production facility at White cement production facility at Riverside CementRiverside Cement•• Kiln stack tested on March 19 Kiln stack tested on March 19 -- 21, 21,

20082008•• Very low levels of hexavalent chromium Very low levels of hexavalent chromium

emittedemitted•• Not enough to account for levels Not enough to account for levels

observed at offsite monitoring locationsobserved at offsite monitoring locations

Bulk Material SamplesBulk Material Samples

Collected Samples from Both Cement Facilities and Batch Collected Samples from Both Cement Facilities and Batch PlantsPlants•• SoilSoil•• Finished productFinished product•• Clinker storage pilesClinker storage piles•• BagBag--house fallhouse fall--outout•• Raw materialsRaw materials

Higher levels of hexavalent chromium found in gray cement Higher levels of hexavalent chromium found in gray cement materialsmaterialsInitially, not enough hexavalent chromium content to Initially, not enough hexavalent chromium content to produce observed concentrations at sampling sitesproduce observed concentrations at sampling sites

Gray Gray Clinker Clinker Outdoor Outdoor Storage Storage PilesPiles

Monitoring Monitoring LocationLocation

Upon Further Analysis…Upon Further Analysis…Separated larger pieces of gray clinker from fine Separated larger pieces of gray clinker from fine dust material using a sievedust material using a sieve

Bulk samples

Sieved Samples(<44 µm)

Cr+6 Cr+6 Location (ppb) (ppb)

Bay A surface 500Bay A sub-surface 750 3980Bay B surface 800 3350Bay B sub-surface 870Bay H surface 1320 6830Bay H sub-surface 2030Bay I surface 1140 2070Bay I sub-surface 1120Bay J surface 1670 15000Bay J sub-surface 1740

•• Fine dust showed much Fine dust showed much higher hexavalent chromium higher hexavalent chromium contentcontent

•• Fine dust is more likely to Fine dust is more likely to become airborne and blow become airborne and blow offsiteoffsite

•• Observed concentrations at Observed concentrations at sampling sites now within sampling sites now within the range of model the range of model predictions

TXI Riverside

predictions

FingerprintingFingerprintingMicroscopically examined gray clinker fine dust Microscopically examined gray clinker fine dust and particles on the deposition platesand particles on the deposition plates

Deposition Plate Adjacent to Deposition Plate Adjacent to TXI Riverside CementGray Clinker Fine DustGray Clinker Fine Dust TXI Riverside Cement

More FingerprintingMore Fingerprinting

36-0432 (D) - Gypsum - Ca33-1161 (*) - Quartz, syn - 04-0733 (I) - Portlandite, sy42-0551 (*) - Calcium Silic

13-0272 (N) - Calcium Magnesiu05-0586 (I) - Calcite, syn - CaCOOperations: Y Scale Add 9500.000808109-025 - File: 0808109-025Operations: Y Scale Mul 0.542 | 0807302-004 - File: 0807302-004Operations: Y Scale Add -45750.Glass plate 114-08 - File: Glass p

Operations: Y Scale Add 11000.0Glass plate 120-08 - File: Glass pOperations: Y Scale Add 10500.0Glass plate 118-08 - File: Glass pOperations: Y Scale Add 10000.0Glass plate 116-08 - File: Glass pOperations: Y Scale Add 10500.0Glass plate 121-08 - File: Glass p

Operations: Y Scale Add 6416.660808109-001 - File: 0808109-001Operations: Y Scale Add 9166.660808109-021 - File: 0808109-021Operations: Y Scale Add -1833.30808109-019 - File: 0808109-019Operations: Y Scale Add 7333.330808109-015 - File: 0808109-015

Operations: Y Scale Add 8250.000808109-013 - File: 0808109-013Operations: Y Scale Add 9625.000808109-007 - File: 0808109-007Operations: Y Scale Add 8708.330808109-006 - File: 0808109-006Operations: Y Scale Add 8250.000808109-023 - File: 0808109-023

Lin

(Cou

nts)

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000

120000

130000

140000

150000

160000

2-Theta - Scale9 10 20 30 40

114-08 Fleetwood

120-08 Aramark

121-08 Plumbers Union

118-08 Rubidoux Station

116-08 Wilson residence

(025) Bay J T-II clinker sub-surface

(019) Bay G Block clinker surface

(006) Bay A T-II clinker sub-surface

(021) Bay H T-II clinker surface

(023) Bay I T-II clinker surface

(007) Bay B T-II clinker surface

(015) Bay E Scrap clinker,soil,cement surface

(013) Bay E Dirt and scrap surface

(001) Spillage from Kiln #1

LN 0807302-004 Gray cement

calcium hydroxide

calcium silicates

XX--Ray Ray Diffraction Diffraction (XRD) to (XRD) to measure measure chemical chemical composition composition and crystal and crystal structurestructureCalcium Calcium hydroxide a hydroxide a marker for fine marker for fine clinker dustclinker dustFound on Found on deposition deposition plates nearerplates nearer

NearPlates

Fine Clinker

Dusts

DistantPlates

Calcium Hydroxide

ConclusionsConclusionsFine clinker dust from TXI Riverside Cement Fine clinker dust from TXI Riverside Cement is a source of airborne hexavalent chromiumis a source of airborne hexavalent chromiumCal Portland Cement emissions appear to be Cal Portland Cement emissions appear to be less than TXI Riverside Cementless than TXI Riverside Cement•• Better dust controlBetter dust control•• Indoor storage of clinkerIndoor storage of clinker•• Longer distance between potential emission points Longer distance between potential emission points

and the fencelineand the fenceline•• Additional monitoring will be conductedAdditional monitoring will be conducted

Cancer RiskCancer RiskLifetime cancer risk based on 70 years of Lifetime cancer risk based on 70 years of continuous exposurecontinuous exposureBasinBasin--wide average is ~1200 in one millionwide average is ~1200 in one millionOnly 16 weeks of data collected to dateOnly 16 weeks of data collected to dateImmediately adjacent to the siteImmediately adjacent to the site

•• 250 to 500 in one million250 to 500 in one millionSimilar to risk next to a busy freeway, a rail Similar to risk next to a busy freeway, a rail yard or a chrome plating facilityyard or a chrome plating facilityCancer risk calculations method under reviewCancer risk calculations method under review

Cancer Risk Calculations Cancer Risk Calculations Method Under ReviewMethod Under Review

Children may be more susceptible Children may be more susceptible from exposures to cancer causing from exposures to cancer causing substancessubstancesCal/EPA reviewing cancer risk Cal/EPA reviewing cancer risk potenciespotencies•• Proposal to apply additional weighting factors for Proposal to apply additional weighting factors for

childhood exposures childhood exposures •• Next steps: review by public and by State Next steps: review by public and by State

Scientific Review PanelScientific Review Panel•• If adopted estimated cancer risk would increase by If adopted estimated cancer risk would increase by

1.7 times from lifetime exposure to cancer causing 1.7 times from lifetime exposure to cancer causing substancessubstances

Hexavalent Chromium Regulatory Levels and Monitored Levels

0

1,000

2,000

3,000

4,000

5,000

6,000

OSHA NIOSH CalEPAReferenceExposure

Level

RiversideCement*

CalPortland*

WestRiversideMATES III

Basin Avg.MATES III

ng/m3

200

1000

5000

1.46 0.39 0.20

*Samples taken adjacent and downwind of cement facilities

0.35

Immediate Control MeasuresImmediate Control Measures

Aggressive action to reduce the hexavalent Aggressive action to reduce the hexavalent chromium emissions from cement handling chromium emissions from cement handling and production, and to lower the risk levels and production, and to lower the risk levels in the communityin the community•• Notices of Violation issued for visible dust Notices of Violation issued for visible dust

emissionsemissions•• Continued and additional sampling in the Continued and additional sampling in the

community for hexavalent chromium and dust community for hexavalent chromium and dust (PM10)(PM10)

•• Ongoing field surveillance and inspectionsOngoing field surveillance and inspections•• Elimination of outdoor storage of clinkerElimination of outdoor storage of clinker

Airborne Hexavalent Chromium Airborne Hexavalent Chromium Concentrations through July 23, 2008Concentrations through July 23, 2008

0.001.00

2.003.004.00

5.006.00

7.008.00

2/13/0

8

2/27/0

8

3/12/0

8

3/26/0

8

4/9/08

4/23/0

8

5/7/08

5/21/0

8

6/4/08

6/18/0

8

7/2/08

7/16/0

8

Site #1 (TXI Riverside) Site #6 (Cal Portland)

Further Control MeasuresFurther Control MeasuresModify TXI permit requirementsModify TXI permit requirementsAmend SCAQMD Rule 1156 to further Amend SCAQMD Rule 1156 to further reduce particulate emissions from reduce particulate emissions from cement plantscement plantsAdopt new SCAQMD rule to reduce Adopt new SCAQMD rule to reduce Cr+6 emissions from cement plantsCr+6 emissions from cement plantsSuggest inclusion of Cr+6 standards Suggest inclusion of Cr+6 standards in NESHAP Subpart LLLin NESHAP Subpart LLL