ACRYLONITRILE A Briefing on the Compound and Issues Surrounding It

OUTLINE What is Acrylonitrile (ACN)? What is Acrylonitrile (ACN)? Why is ACN Important? Why is ACN Important? Issues Surrounding ACN Data Issues Surrounding ACN Data  Monitoring  Sources Next Steps Next Steps

ACRYLONITRILE CHEMICAL FORMULA What is ACN?

CHARACTERISTICS Man-made synthetic chemical: no natural sources Man-made synthetic chemical: no natural sources In pure form, polymerizes spontaneously and violently in the presence of sunlight In pure form, polymerizes spontaneously and violently in the presence of sunlight Half-life of approx. 50 hrs in ambient air Half-life of approx. 50 hrs in ambient air Reacts with hydroxyl radicals and oxygen Reacts with hydroxyl radicals and oxygen

OUTLINE What is Acrylonitrile (ACN)? What is Acrylonitrile (ACN)? Why is ACN Important? Why is ACN Important? Issues Surrounding ACN Data Issues Surrounding ACN Data  Monitoring  Sources Next Steps Next Steps

Why is ACN Important? RISK FROM ACRYLONITRILE 2004 statewide annual average was 0.48 ppb, a risk of 300 in a million 2004 statewide annual average was 0.48 ppb, a risk of 300 in a million 2004 South Coast annual average was 0.52 ppb, a risk of 320 in a million 2004 South Coast annual average was 0.52 ppb, a risk of 320 in a million Risk from diesel pm is estimated at 300 – 650 in a million Risk from diesel pm is estimated at 300 – 650 in a million Risk from benzene and butadiene together is 83 in a million Risk from benzene and butadiene together is 83 in a million

Why is ACN Important?

OUTLINE What is Acrylonitrile (ACN)? What is Acrylonitrile (ACN)? Why is ACN Important? Why is ACN Important? Issues Surrounding ACN Data Issues Surrounding ACN Data  Monitoring  Sources Next Steps Next Steps

Issues Surrounding ACN Data: Monitoring BACKGROUND Started in July, 2003, MLD SOP066 Started in July, 2003, MLD SOP066 Samples in canisters collected over 24 hrs 1-in-12 days in regular TAC network using regular samplers in place (not cleaned) Samples in canisters collected over 24 hrs 1-in-12 days in regular TAC network using regular samplers in place (not cleaned) Analyzed by preconcentration GC/MS Analyzed by preconcentration GC/MS NIST calibration standard used NIST calibration standard used Lab results confirmed independently by Dr. Rasmussen Lab results confirmed independently by Dr. Rasmussen

Issues Surrounding ACN Data: Monitoring DATA ANALYSIS Maximum concentrations found in the summer Maximum concentrations found in the summer Maximum concentrations found during the periods of highest temperature Maximum concentrations found during the periods of highest temperature No correlation with auto exhaust pollutants No correlation with auto exhaust pollutants Concentrations in 12 other states found to be greater than in California Concentrations in 12 other states found to be greater than in California

Issues Surrounding ACN Data: Monitoring

SAMPLING ISSUES Parallel monitoring by ARB and SCAQMD at LA N Main in Fall of 2006 Parallel monitoring by ARB and SCAQMD at LA N Main in Fall of 2006 Samples collected by ARB contained detectable concentrations of acrylonitrile Samples collected by ARB contained detectable concentrations of acrylonitrile Samples collected by SCAAQMD contained no detectable acrylonitrile Samples collected by SCAAQMD contained no detectable acrylonitrile Possibilities: ARB sampler creating acrylonitrile or SC sampler destroying it Possibilities: ARB sampler creating acrylonitrile or SC sampler destroying it

Issues Surrounding ACN Data: Monitoring ARE THE DATA REAL? Nist standard used, lab cross-checks confirm can concentrations, stable in cans Nist standard used, lab cross-checks confirm can concentrations, stable in cans Numerous sources identified Numerous sources identified Sampler checks show no generation Sampler checks show no generation TTP audits show losses in SCAQMD samplers TTP audits show losses in SCAQMD samplers Past experience with canisters show losses unless active sites are passivated Past experience with canisters show losses unless active sites are passivated

Issues Surrounding ACN Data: Monitoring RESOLUTION OF DIFFERENCE Investigations narrowed the differences to the samplers used by SCAQMD and ARB Investigations narrowed the differences to the samplers used by SCAQMD and ARB Samplers are identical, except that the ARB samplers have been the field for over 15 years, whereas SCAQMD samplers are cleaned prior to each use Samplers are identical, except that the ARB samplers have been the field for over 15 years, whereas SCAQMD samplers are cleaned prior to each use TTP audits show ACN losses with SCAQMD samplers TTP audits show ACN losses with SCAQMD samplers

OUTLINE What is Acrylonitrile (ACN)? What is Acrylonitrile (ACN)? Why is ACN Important? Why is ACN Important? Issues Surrounding ACN Data Issues Surrounding ACN Data  Monitoring  Sources Next Steps Next Steps

Issues Surrounding ACN Data: Sources Emission inventory contains little information on emissions Emission inventory contains little information on emissions No acrylonitrile manufacturing use in CA No acrylonitrile manufacturing use in CA Acrylonitrile used in a wide variety of polymers, paints, adhesives, and fibers Acrylonitrile used in a wide variety of polymers, paints, adhesives, and fibers Auto parts Auto parts Polymer extruding operations? Polymer extruding operations?

Issues Surrounding ACN Data: Sources GRAB SAMPLING Grab samples taken in three Sacramento homes: <0.3, 0.6, <0.3 ppb Grab samples taken in three Sacramento homes: <0.3, 0.6, <0.3 ppb Grab sample taken in cab of truck on car lot: 6 ppb Grab sample taken in cab of truck on car lot: 6 ppb Grab sample taken in private garage: 11 ppb Grab sample taken in private garage: 11 ppb It really is there It really is there

Issues Surrounding ACN Data: Sources ABS Polymer 4.4 ug/gm ABS Polymer 4.4 ug/gm ABS Pipe 11 ug/gm ABS Pipe 11 ug/gm ABS Plate 5 ug/gm ABS Plate 5 ug/gm Acrylic glue 47 ug/gm Acrylic glue 47 ug/gm Latex Paint 0.4 ug/gm Latex Paint 0.4 ug/gm Enamel Paint 1.2 ug/gm Enamel Paint 1.2 ug/gm N Gloves 1.5 ug/gm N Gloves 1.5 ug/gm Carpet 0.3 ug/gm Carpet 0.3 ug/gm Sheet Vinyl 0.3 ug/gm Sheet Vinyl 0.3 ug/gm Ceramic Glue 0.2 ug/gm Ceramic Glue 0.2 ug/gm Fingernail Polish 12 ug/gm Fingernail Polish 12 ug/gm FLUX CHAMBER EMISSIONS

Issues Surrounding ACN Data: Sources OTHER PUBLISHED WORK Sampling and Analysis of Volatile Organic Compounds Evolved During Thermal Processing of ABS Composite Resins. Cantos, et. al., JAWMA, 45, Acrylonitrile Source Concentration ug/gm Auto Parts 5.74 Pipe9.75 Refrigeration10.4

OUTLINE What is Acrylonitrile (ACN)? What is Acrylonitrile (ACN)? Why is ACN Important? Why is ACN Important? Issues Surrounding ACN Data Issues Surrounding ACN Data  Monitoring  Sources Next Steps Next Steps

NEXT STEPS New samplers are to be challenged with acrylonitrile to determine the extent of passivation required New samplers are to be challenged with acrylonitrile to determine the extent of passivation required The acrylonitrile working group should be re-activated and efforts to determine sources of acrylonitrile be continued The acrylonitrile working group should be re-activated and efforts to determine sources of acrylonitrile be continued Other groups nationally (NATTS) should be advised Other groups nationally (NATTS) should be advised