PRINCIPLES, ASSUMPTIONS, AND DATA REQUIREMENTS FOR CHEMICAL MASS BALANCE CMB RECEPTOR MODELS

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PRINCIPLES, ASSUMPTIONS, AND DATA REQUIREMENTS
FOR CHEMICAL MASS BALANCE (CMB) RECEPTOR MODELS
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Purposes of CMB

• Quantify contributions of source types to
  receptor concentrations.
• Separate primary from secondary components.

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Chemical Mass Balance

• Equation
• Input
• Ambient concentrations (Cj)and uncertainties
  (sCj),source composition (Fij),and
  uncertainties (sFij).
• Output
• Source contributions (Sj)and uncertainties
  (sSj).
• Measurements
• Size-classified mass, elements, ions, and carbon
  concentrations on both ambient and source samples.

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Data Base Requirements

• Contains needed observables.
• Available in computerized form (preferably
  IBM/PC).
• Measurement methods and locations are documented.
• Quality control and quality audits.
• Precision and accuracy estimates.
• Validation flags.
• Data base user feedback.

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Source Composition Data Needs

• Profiles for source types.
• Same particle size ranges and species as measured
  at receptor.
• Measurement methods equivalent to those of
  receptor samples.
• Documentation of source characteristics, fuels,
  and operating parameters.
• Source profile uncertainties.
• Profiles are as they would appear at the receptor.

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Ambient Data
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OEPP Sampling Site
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PM chemical composition analysis and the relate
analytical methods
INAA 13 chemical species

• Na, Al, K, Ca, Ti, V, Cr, Mn, Fe,Zn, Se, Br, Sb

Concentration data
XRF1 chemical species
Pb
CHN Analyzer
Organic and Elemental carbons
CMB8 Model
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IINAA analytical error was determined by the
counting of the gramma-ray spectrum
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Result and Discussion
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Total mass input Total mass concentration
-(NH4SO2) -NH4NO3
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SOURCE CONTRIBUTION IN BKK BY CMB8
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CMB Model Assumptions

• Compositions of source emissions are constant
  over the period of ambient and source sampling.
• Chemical species do not react with each other
  (i.e., they add linearly).
• All sources with a potential for significant
  contribution to the receptor have been identified
  and have had their emissions characterized.

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CMB Model Assumptions (continued)

• The number of sources is less than or equal to
  the number of chemical species.
• The source compositions are linearly independent
  of each other.
• Measurement errors are random, uncorrelated, and
  normally distributed.

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CMB Model Application Procedures

• Select source profiles for potential
  contributors.
• Select sources for inclusion in the CMB solution.
• Evaluate goodness of fit measures.
• Finalize source selection.
• Evaluate uncertainties.

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CMB Model Test Results

• Constant compositions can tolerate substantial
  variabilities
• Non-reactive species little known
• All source types identified minor contributors
  can be left out
• Number of sources less than number of species
  the larger the difference the better

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CMB Model Test Results (continued)

• Source contributions linearly independent
  degree depends on variability of source profile
• Measurement error distribution effects unknown

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Conclusions About Air Quality Models

• Every model is a simplification of reality.
• Model results can be no better than the input
  data supplied to the model.
• The application of a single model will supply an
  answer. The application of several models will
  supply doubt.

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Ambient Data
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OEPP Sampling Site
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PM chemical composition analysis and the relate
analytical methods
INAA 13 chemical species

• Na, Al, K, Ca, Ti, V, Cr, Mn, Fe,Zn, Se, Br, Sb

Concentration data
XRF1 chemical species
Pb
CHN Analyzer
Organic and Elemental carbons
CMB8 Model
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IINAA analytical error was determined by the
counting of the gramma-ray spectrum
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SOURCE CONTRIBUTION IN BKK BY CMB8
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Ambient Sample Collection
Two sets of Andersons Dichotomous air samplers
Ban Hua Fai Receptor site

Power plantUnits 4-13
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Chemical composition analysis
Filters
Teflon
Quartz fiber filter
punch out O.5 cm diameter
Elemental analysis
TC
OC
ICP-MS/JESC
Carbon analysis
IC
CHNS/O-analyser
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Analytical methods for chemical compositions
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Receptor Model used in this study
Chemical Mass Balance Model
Factor analysis -Multiple Regression model

US. EPA. CMB8
SPSS and Excel
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Source apportionmentResults and discussions
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Sampling date
Variation of PM10 concentrations at Ban Hua Fai
during the sampling period
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Scatter diagram between PM10 observed vs.
automated beta-ray PM10
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Scatter diagram of PM10 observed vs. SO2 , NOx
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Average Concentrations at Receptor Site
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FA-MR Model results
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Diagram of FA-MR Method
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Factor score equation
Absolute factor score calculation
1. Calculation of the normalised value for
the case that each elemental is 0
2. Calculation of the absolute zero score
3. Calculation of the absolute factor score
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MRL between AFS vs. PM concentration
mass concentration of sample k
regression constant(intercept)
Source contribution estimation
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Varimax rotated factor loading and possible
source types
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Correlation coefficient between the factor scores
and pollutant gas concentrations
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Biomass burning automobile
Soil and or /road dust
The pollution rose of each factor at receptor
station
Secondary pollutants
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Source contribution of PM10 at the receptor site
by FA-MR calculation
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CMB8 Model Results
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Chemical compositions input in CMB8 Model
ICP-MS 9 chemical species

• Mg, Al, K, Ca, V, Mn, Fe, As, Sr

Concentrationdata
CHNS/O Analyzer
Organic and Elemental carbons
CMB8 Model
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Average concentrations of elemental compositions
input into the CMB8 model
Note a average from 31 samples and the under
detection limit concentrations were replaced by
one-tenth of LOD.
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Source profile inputs for CMB8 calculation
Profile no. N153LDD Zielinska et al. (1998)
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Initial CMB8 running
mass 102.7, R2 1.00, Chi2 0.10 d.f.
3 Fitting species Al, K, Ca, V, As, Sr,
OC,
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Time variation of source contribution in the
receptor site
Sampling date
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Time variation of mass, R2 and Chi2 of CMB8
calculation
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The regression between observed vs. calculation
of PM10 element concentration
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The regression between observed vs. calculation
of PM10 element concentration
Mg
R2 0.6648
R2 0.6895
As
R2 0.1221
R2 0.5173
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The regression between observed vs. calculation
of PM10 mass concentration
Calculation
Observed
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Relative contribution of source profiles derived
from CMB8 estimation
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Average-conc. Run vs. Average of Daily-conc. Runs
CMB8 calculations
Running with average conc. from 31 sample
Average from daily conc. running
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Comparison of FA-MR and CMB8 mass calculations
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Correlations between FA-MR and CMB Models
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Mini Vol Portable Air Sampler (Air Metrics)Flow
rate 5 L/min
2 ??? ????????
PTFE filter
Quartz-fibre filter
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Gilibrator flow cell S/N 0304146-H
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Gilibrator flow cell S/N 0304146-H Calibration
data Sampler ID Mini-Vol SN 2149 Date29/04/25
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Rotameter Reading flow (L/min)
Gilibrator flow cell (L/min)
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Gillibrator flow cell ??? rotameter
Gilibrator flow cell (L/min)
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Quartz
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System Performance Guidelines
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Collocated Comparisons(same sampler type PM10
µg/m3 )
???????????
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Collocated Comparisons(difference sampler types
PM10 µg/m3 )
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Chemical composition analysis
Filters
Quartz fiber filter
Teflon
punch out O.5 cm diameter
Elemental analysis
TC
IC
XRF 33 ????
OC
CHNS/O-analyser
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FA-MR Results
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CMB8 Model
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