ADVANCES IN MONITORING METHODS FOR AIRBORNE PARTICLES Philip K. Hopke Department of Chemical...
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ADVANCES IN MONITORING METHODS
FOR AIRBORNE PARTICLES
Philip K. HopkeDepartment of Chemical Engineering, Clarkson University, Potsdam, NY 13699-5705 USA
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Air Quality Standards
• In 1997, the U.S. Environmental Protection Agency promulgated new National Ambient Air Quality Standards (NAAQS) for airborne particulate matter.– New standards were established for PM2.5
– Revised standards were set for PM10
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Air Quality Standards
• The PM2.5 standards were set as:
– Annual arithmetic average standard• 15 µg m-3 • Averaged over three years
– Each quarter must have 75% collection– Quarterly averages are averaged over the 3 years
• Value >15.1 µg m-3 is in non-attainment.
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Air Quality Standards
• The PM2.5 standards were set as:
– 24-Hour standard • 65 µg m-3 • 98th Percentile Standard based on 3-years of data
– Determine the 98th percentile value for each of the three years
– Average these three values– If it is greater than 66 µg m-3, the site is in non-attainment
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Air Quality Standards
• The PM2.5 standards were set to be:• Measured with a standard design Federal
Reference Method sampler• Samplers deployed based on population density• Measurements at least every third day• Teflon filters
– Equilibrated and weighed prior to and after exposure.
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Air Quality Standards
• The PM10 standards were set to be:
– Maintain the 1987 annual arithmetic mean value of 50 µg m-3
– Set a new 24-hour standard of 150 µg m-3 which is the same as the 1987 value, but now as the 99th percentile value
– Three years of data needed as in the PM2.5 standard
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Air Quality Standards
• Lawsuit was filed against the Administrator by the American Truckers Associations with a number of co-plaintiffs
• Alleged that the EPA had exceeded their authority by creating the PM2.5 standard as well as raising a number of points with respect to the new 8-hour O3 standard that was also promulgated in 1997.
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Air Quality Standards
• The PM10 NAAQS was promulgated to protect public health from coarse particles that would not be part of PM2.5,
• The suit alleged PM10 to be illegal since it included PM2.5 and the effects of the two cannot be adequately separated.
• PM10 is thus not an effective indicator of coarse particle exposure
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Air Quality Standards
• A 3 judge panel of the Court of Appeals for the Third Circuit (Washington, DC) upheld the entire suit by a 2 to 1 majority
• EPA chose to contest the decision except for the part of regarding the invalidation of the PM10 standard.
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Air Quality Standards
• The Supreme Court found for the EPA and remanded the case back to the Court of Appeals with specific instructions regarding the outcome
• The Court of Appeals then dismissed all of the remaining parts of the suit.
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Air Quality Standards
• Thus, at this time the NAAQS in the United States include the– 1997 PM2.5 standard (both annual average
and 24-hour standards).– 1997 eight-hour ozone standard
– 1987 PM10 NAAQS remains in effect since it was not part of the lawsuit and thus, is not affected
– However, a new coarse particle standard will be set in this round of NAAQS review.
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PM2.5 Monitoring Program PM2.5 Program Objectives: Why Monitor?
Comparison With Air Quality Standards
Development of Emission Control Strategies
Support Modeling & Emissions
Continued Assessment of Strategies and Trends
Public Awareness
Research On:
Atmospheric Processes and Emissions
Source-Receptor Relationships
Health Effects/Exposure
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Supersites
Mass Monitoring Network >1100 Sites
7 sites
300 State Sites
+
150 IMPROVE
Speciation Network
EPA PM2.5
Monitoring Network
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Airborne Mass Concentration Measurement
• Approved method is the Federal Reference Sampler
• Equivalent manual samplers can be developed from the same sampler plans
• Very difficult to develop an equivalent continuous sampler because of the stringent requirements
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FRM Sampler• Designed to
– Have sharp cutpoint– Volumetric flow control– Have high precision
• However, it has– Unknown loss of semivolatile components
• Ammonium nitrate• Organic compounds
• Thus, it has unknown accuracy and it is only right by REGULATION!
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FRM Monitoring Network
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FRM Sampler
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Problems with FRM
• Accuracy
• Cost– High labor and time cost
• Equilibration• Transport to site• Weighing
• Only 33% of the days sampled even when everything goes right!
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Problems with FRM
• WINS impactor uses oil to prevent particle bounce– Freezes in the winter although a
replacement oil type has now been approved.
• WINS impactor can now be replaced by the sharp cut cyclone– No oil– Less maintenance
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Continuous Mass Monitors
• Need systems that provide continuous measurements of the particle mass– Lower operating costs– Complete data
• More accurate determination of attainment status
– Provide better data for epidemiology and atmospheric process understanding.
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Continuous Mass Monitors
• Need a response to collected particle mass– TEOM– Beta Attenuation Monitors– Pressure across over a filter
• Commercial systems are available
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Continuous Mass Monitors
• Problem is not with the detector, but deciding what to measure
• Water associated with the particle is assumed to be non-toxic and thus, should be removed.
• Desire to match the FRM measured values
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Continuous Mass Monitors
• How to remove the water without removing semivolatiles?
• Do we want to match the FRM when we know it is inaccurate?
• What is currently available?
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30ºC TEOM with SES
• Operate TEOM at 30ºC
• Sample Equilibration System uses a Nafion dryer to remove water
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Continuous Aerosol Mass Monitor (CAMM)
• Pressure drop over a filter
• Uses Nafion® dryer
• Attempts to match FRM values
• Has a serious problem if there is much mass in the 1.5 to 2.5 µm range.
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Research Systems
• Real-time Aerosol Mass System (RAMS)– Developed by Delbert Eatough at BYU– Uses a concentrator to increase the S/N ratio– Dual monitoring system
The problem is to deal with both the positive and negative artifacts
Adsorption of organics on filter
Volatilization of ammonium nitrate and SVOCs
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Differential Systems
• RAMS is too large and too complex to be a useful monitoring tool.
• However, suggested the idea of a differential system in which comparisons are made between collection of gases and particles and removal of particles. This comparison permits the estimation of artifacts, both positive and negative
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Differential TEOM
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Filter Dynamics Measurement System (FDMS)
• The Filter Dynamics Measurement System quantifies both the volatile and non-volatile components of particulate matter (PM), and reporting the combination as a mass concentration result by measuring the volatile portion of the sample independently from the total incoming sample, and accounting for this fraction in calculating the PM mass concentration.
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Continuous Mass MonitorsX Y Intercept slope r # samples
Precision
RAAS2 RAAS -0.57 0.98 1.0 33
And-BAM3 And-BAM 0.69 0.98 0.98 99
Met-BAM4 Met BAM -1.19 0.98 1.0 105
FDMS5 FDMS 0.88 1.04 0.99 55
CAMM6 CAMM 2.32 0.97 0.91 96
Accuracy
RAAS And-BAM -1.32 1.02 0.98 102
RAAS Met-BAM -1.58 1.03 1.0 102
RAAS FDMS 3.73 1.01 0.99 102
RASS CAMM 9.79 0.68 0.87 93
2
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Continuous Mass Monitors
• New guidelines are being developed to permit regional relationships to be developed between the continuous monitor and a collocated FRM.
• We should start to see a significant number of continuous monitors in the compliance monitoring network within the next 1 to 2 years.
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Speciation Network
• Chemical composition data to support
• ~190 PM2.5 filter-based chemical speciation monitoring sites operating, or identified and scheduled to start operating, by December 31, 2001
• 110 IMPROVE sites and 34 IMPROVE protocol sites
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Speciation Network
• XRF for elements
• Ion Chromatography for major anions and cations
• OC/EC using a modified NIOSH 5040 method
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Speciation Network Data• Trends in composition over time
• Source apportionment for State Implementation Plan development
• Potential for epidemiology on chemical species or apportioned source contributions
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Continuous Chemical Data
• Improved time resolution permits identification of atmospheric process details,
• Identification of plumes from point sources,
• Improved source resolution, and
• Better air quality planning.
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Continuous Chemical Measurements• Continuous measurement of chemical
constituents (commercial systems)– Sulfate– Nitrate– OC/EC– Single Particle Mass Spectrometry
• Research Systems– Particle into Liquid System (PILS)– Semi-continuous Elements in Aerosol System (SEAS)
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Illustrative Results
• Rochester, NY
• Sampled through a 4” duct inlet
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Illustrative Results
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• Developed by John Ondov at the University of Maryland at College Park
• Uses steam injection to cause hygroscopic growth
• Collected samples can then be analyzed
• Half-hour time resolution is possible
Semi-continuous Elements in Aerosol System (SEAS)
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Semi-continuous Elements in Aerosol System (SEAS)
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SEAS
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QUESTIONS?
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