ENV 4101/5105 Elements of Air Pollution

Reading: Chap 7.1 & 7.2

Air Quality
Monitoring

http://www.statcan.ca/english/freepub/16-254
-XIE/2007000/tablesgraphs/figure3-en.htm

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 Air Quality Monitoring
Monitoring Considerations
Manual vs. automated (real-time, continuous) monitoring
Sampling time
Federal reference method (FRM) vs. equivalent method (EM)
Monitoring of Ambient Air Pollutants
SO2, NOx, CO, O3
Hydrocarbons
PM10, PM2.5
Source Sampling and Monitoring
Sampling train
Isokinetic sampling
Quality Assurance Programs
Quality Assurance
Quality Control
Air Quality Monitoring Network
Whats the use of ambient air quality monitoring data?
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 Monitoring Considerations
Sampling location: limited number of fixed site
monitors whose locations reflect objectives of air
quality monitoring program
What are the objectives?

Examples of criteria for selecting ambient sampling locations?

Lower limit of detection (LOD): a sufficient amount of
pollutant must be collected, f(sampling rate, duration)
Integrated sampling vs. real-time sampling
Area sampling vs. personal sampling
Collection efficiency of the instrument:
Low flow rate for gas-phase contaminants (< 1 L/min)

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 Differences in averaging times
associated with real-time data

Which duration should you use?

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 National Ambient Air Quality Standards
Pollutant Primary Stds. Averaging Times Secondary Stds.
CO 9 ppm (10 mg/m3) 8-hour(1) None

35 ppm (40 mg/m3) 1-hour(1) None

Pb 1.5 g/m3 Quarterly Ave Same as Primary
NO2 0.053 ppm (100 g/m 3) Annual (Arith. Mean) Same as Primary

PM10 Revoked(2) Annual(2) (Arith. Mean)

150 g/m3 24-hour(3)
PM2.5 15.0 g/m3 Annual(4) (Arith. Mean) Same as Primary
35 g/m3 24-hour(5)
O3 0.08 ppm 8-hour(6) Same as Primary
0.12 ppm 1-hour(7) (Applies only in Same as Primary
limited areas)
SO2 0.03 ppm Annual (Arith. Mean) -------
0.14 ppm 24-hour(1) -------
------- 3-hour(1) 0.5 ppm (1300 g/m3)

http://www.epa.gov/air/criteria.html
Why different durations?
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 Federal Reference Methods for Criteria Pollutants
Pollutant Reference Method
SO2 Spectrophotometry (pararosanilne method)

NO2 Gas-phase chemiluminescence

CO Nondispersive infrared photometry

O3 Chemiluminescence

NMHCs Gas chromatography FID (flame ionization detection)

PM10 Performance-approved product

PM2.5 Performance-approved product

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 SO2
FRM - Spectrophotometry (pararosanilne method)
Air sample potassium tetrachloromercurate solution
HgCl2SO3-2 react with HCHO and colorless pararosaniline
hydrochloride red-violet product measured
spectrophotometrically SO2 concentration

EM FT- IR Spectrometry
(Absorption of IR by SO2 in
the air SO2 concentration)

http://clu-in.org/programs/21m2/openpath/op-ftir/images/exhibit3.gif

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 SO2
EM UV Fluorescence
1) UV light excites SO2 to a higher energy state
SO2 + hv1 SO2*
2) Decay of the excited SO2*, emitting a characteristic radiation
SO2* SO2 + hv2

www.cse.polyu.edu.hk/~airlab/so2.jpg

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 NO NO2 NOx
FRM Gas-Phase Chemiluminescence
Chemiluminescence: emission of light
from electronically excited chemical
species formed in chemical reactions.
NO + O3 NO2* + O2
NO2* NO2 + hv

Measurement of NO2: conversion of NO2 to

NO, and subsequent measurement by
chemiluminescence.
2NO2 + Mo 3 NO + MoO3

Possible interference: N-containing

compounds higher measured NO2
EM FT- IR Spectrometry www.k2bw.com/images/chem.gif

Can you design an instrument that can measure the

concentration of both NO and NO2 in the air?
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 CO
FRM Nondispersive Infrared (NDIR) spectrometry
CO strongly absorbs infrared energy at certain wavelengths.

Detection device: two cylindrical cells, a sample and a reference cell.

Difference in infrared energy in the two cells concentration of CO

CO

Sample Reference
Cell ~ IR ~ Cell

Detection
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 O3
FRM Chemiluminescence
Light emissions produced on reaction of O3 with ethylene (C2H4).

C2H4 flammable replaced by Rhodamine B dye embedded in a disk

Rhodamine B does not attain a stable baseline rapidly after exposure to O3

EM UV Photometry
Absorption of UV light (254 nm) by O3 and subsequent use of
photometry to measure the reduction of UV energy
O3

UV light (254 nm) Detector

What would cause an

O3
interference on a UV
photometry O3 monitor?
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 NMHCs
FRM Gas Chromatography - FID

Intensity
Time

Stationary and mobile phases

GC-Detector:
Generate an electronic signal when a gas other than the carrier gas elutes from the column.

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 NMHC
FID Flame Ionization Detection:
Combustion of organic substances
Positive ions (+) and electrons (-) are formed when
burned change in current
Mass sensitive rather than
concentration sensitive

http://teaching.shu.ac.uk/hwb/chemistry/tutorials/chrom/gaschrm.htm
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 Particulate Pollutants
Impaction and filtration are the
primary PM collection principles
Measure the weight of exposed
and clean filters
High-volume sampler (Hi-Vol)
Typical sampling duration 24 h
Animation
PM10 Sampler PM10 Impactor
Remove particles > 10 m by
impaction on a greased surface
Particles < 10 m collected on a
quartz glass fiber filter
What does the PM10 sampler
PM10 sampler with size-selective inlet measure? Number or mass
http://www.recetox.muni.cz/images/airsag/PM10.jpg concentration of particles?

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 Dichotomous Sampler
Animation
Virtual Impactor

TEOM Series 1400ab

Ambient Particulate Monitor
Thermo Electron Co.

Equivalent method: TEOM

Measure PM10, PM2.5, TSP
http://crac.ucc.ie/images/sampler1.jpg
Tapered element oscillating
microbalance
How can a Dichotomous sampler Real-time measurement of
measure coarse (PM2.5-10) and fine particle mass collected on a
filter
(PM2.5) particles?

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 Animation Aerosol flow In
Cascade Impactor
Cascade Impactor

Clean air out

How can we collect

different sizes of particles
using cascade impactor?
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 Source Sampling and Monitoring

Stack Sampling of PM Isokinetic Sampling

1) Probe inserted into the stack 1) Particles inertial forces
2) Temperature sensor 2) Samples must be collected at the
3) Pitot tube gas velocity and flow rate same rate of low as the stack gas
4) Two-module sampling unit

Whats the use of source emission data?

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 Isokinetic Sampling

Fig 8 -2, Aerosol Measurement, 2nd Edition, 2001

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 Continuous Emission Monitoring (CEM)
Certain utilities and industrial sources are required
to measure stack emission continuously
SO2, NO2, opacity, CO2, TRS, H2S, Hg

Opacity
Compare plume darkness to
Ringlemann chart by trained
smoke readers
Averages of measurements of
or minute over an hour
Simple, low cost, legal
acceptance
Ringlemann chart

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 Accuracy, Precision and Bias
O A
Relative Error: Er % 100 Bias
A

Coefficient of variation: CV % 100 Precision
X

Accuracy is a combination of random (precision) & systematic (bias)

errors. Which of the 3 cases has the highest accuracy? Why?
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 Calibration
Often used for adjusting bias-type errors
Measured values are compared to standard reference
values (for pollutant concentration) or standard airflow
measuring techniques/devices (for volume air flow)
Primary vs. secondary standard for flow: traceable to
the National Institute of Standards and Technology
(NIST)
Primary: bubble meter
Secondary: wet or dry test meters calibrated by bubble meter
Gas standards: traceable to a NIST reference material
CO, SO2, NO2, NO: available in cylinder gas or permeation tubes
O3: NIST certified O3 generator

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 Quality Assurance Programs

Goal: Valid and reliable air quality monitoring data

Quality Assurance (QA)

Setting policy and overseeing management controls
Planning, review of data collection activities and data use
Setting data quality objectives, assigning responsibilities,
conducting reviews, and implementing corrective actions

Quality Control (QC)

Technical aspects of data quality programs
Implementation of specific QC procedures:
calibrations, checks, replicate samples, routine self-
assessment, and audits

It is federal rule to document QA/QC efforts !

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 Air Quality Monitoring Network
State and Local Air Monitoring Stations (SLAMS)
Highest pollutant concentrations
Representative concentrations in areas of high population density
Impact of major emission sources
Regional background concentrations
Extent of pollutant transport among populated areas
Welfare-related impacts in more rural and remote areas
National Air Monitoring Stations (NAMS)
Urban area, long-term air quality monitoring network
Air quality comparisons and trends analysis
Photochemical Assessment Monitoring Stations (PAMS)
Monitor O3 and photochemical air pollutants
Clean Air Status and Trends Network (CASTNet)
Primary source for rural O3 level and dry atmospheric deposition
National Atmospheric Deposition Program (NADP)
Assess the problem of atmospheric deposition and its effects on aquatic
and terrestrial ecosystems (H+, NH4+, SO42-, NO3-, Cl-, Ca2+, Mg2+, K+, Hg)
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 Quick Reflections
Monitoring Considerations
Manual vs. automated (real-time, continuous) monitoring
Sampling time
Federal reference method (FRM) vs. equivalent method
(EM)
Monitoring of Air Pollutants
SO2, NOx, CO, O3
Hydrocarbons
PM10, PM2.5
Source Sampling and Monitoring
Sampling train
Isokinetic sampling
Quality Assurance Programs
Quality Assurance
Quality Control
Air Quality Monitoring Network

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