Introduction to Model 1130/35 Automated Ambient Air Speciated Mercury Monitor F.H. Schaedlich Rev:...
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Transcript of Introduction to Model 1130/35 Automated Ambient Air Speciated Mercury Monitor F.H. Schaedlich Rev:...
Introduction to Model 1130/35Introduction to Model 1130/35Automated Ambient Air Automated Ambient Air
Speciated Mercury Monitor Speciated Mercury Monitor
Introduction to Model 1130/35Introduction to Model 1130/35Automated Ambient Air Automated Ambient Air
Speciated Mercury Monitor Speciated Mercury Monitor
F.H. Schaedlich F.H. Schaedlich
ekran Inc. ekran Inc.
Rev: 1.11 November 3, 2003Rev: 1.11 November 3, 2003
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 2
AcknowledgementsAcknowledgements Matt Landis US EPA 1
Robert K. Stevens Florida DEP 2a
Tom Atkeson Florida DEP 2b
Eric Prestbo Frontier Geosciences 3
Steve Lindberg Oak Ridge Nat’l Labs 4
Gerald Keeler University of Michigan 5
1 1 Research Triangle Park, NC 27711Research Triangle Park, NC 277112a2a At US EPA, Research Triangle Park, NC 27711At US EPA, Research Triangle Park, NC 277112b2b Tallahassee, FL Tallahassee, FL 33 414 Pontius Ave. N., Suite B, Seattle, WA 98109414 Pontius Ave. N., Suite B, Seattle, WA 9810944 PO Box 2008, Oak Ridge, TN 37831-6038PO Box 2008, Oak Ridge, TN 37831-60385 5 School of Public Health, 109 Observatory Street, MI 48109.School of Public Health, 109 Observatory Street, MI 48109.
Total Gaseous Mercury Total Gaseous Mercury MonitoringMonitoring
Part 1Part 1
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 4
Why measure parts per Why measure parts per QuadrillionQuadrillion of Mercury ?of Mercury ?
Mercury is one of the most potent neurotoxins Mercury is one of the most potent neurotoxins knownknown
Bio-accumulates up the food chain by factors of Bio-accumulates up the food chain by factors of up to up to 10,000,00010,000,000 timestimes Sub-ppt levels in air can accumulate to toxic ppm Sub-ppt levels in air can accumulate to toxic ppm
levels in fishlevels in fish
Levels are increasing worldwideLevels are increasing worldwide
Long life in the atmosphere means that mercury Long life in the atmosphere means that mercury emissions are of emissions are of globalglobal concern concern
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 5
Total Gaseous Mercury MonitoringTotal Gaseous Mercury Monitoring
Originally implemented manuallyOriginally implemented manually Gold coated silica field cartridgesGold coated silica field cartridges Analysis using dual stage thermal desorption Analysis using dual stage thermal desorption
with CVAFS (atomic fluorescence) detectionwith CVAFS (atomic fluorescence) detection
Gold preconcentration with AA (atomic Gold preconcentration with AA (atomic absorption) detection had been shown to absorption) detection had been shown to be subject to serious artifacts when be subject to serious artifacts when attempting to measure ambient levelsattempting to measure ambient levels
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 6
Model 2537A Mercury AnalyzerModel 2537A Mercury Analyzer Automated implementation of gold/AF manual methodAutomated implementation of gold/AF manual method
Instrument protected by US and international patentsInstrument protected by US and international patents
Has largely supplanted manual cartridge methodsHas largely supplanted manual cartridge methods
Provides continuous total gaseous (Provides continuous total gaseous (TGMTGM) readings with ) readings with update rate as low as update rate as low as 2.52.5 minutes minutes
Detection limit Detection limit < 0.1 ng/m< 0.1 ng/m33 (5 min. samples)(5 min. samples)
Automatic recalibration with internal HgAutomatic recalibration with internal Hg00 permeation permeation sourcesource
Capable of unattended operation for extended periodsCapable of unattended operation for extended periods
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 7
Model 2537A AnalyzerModel 2537A Analyzer
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 8
Principles of OperationPrinciples of Operation
Mercury in sample gas is preconcentrated Mercury in sample gas is preconcentrated onto (pat’d) pure gold cartridgeonto (pat’d) pure gold cartridge
Adsorbed mercury is thermally desorbedAdsorbed mercury is thermally desorbed
Detected by atomic fluorescence detectorDetected by atomic fluorescence detector
Two cartridges are used to alternately Two cartridges are used to alternately sample and desorbsample and desorb No gaps in data streamNo gaps in data stream
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 9
Flow Diagram of Model 2537A Flow Diagram of Model 2537A Mercury Analyzer Mercury Analyzer (Pat’d)(Pat’d)
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 10
Pure Gold Cartridge Pure Gold Cartridge (Pat’d)(Pat’d)
Pure gold only is used as adsorbentPure gold only is used as adsorbent No quartz wool or silicaNo quartz wool or silica No memory effectNo memory effect
Extremely durable designExtremely durable design Lasts for years of continuous useLasts for years of continuous use
Cartridge design is protected by separate Cartridge design is protected by separate US and international patentsUS and international patents
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 11
Pure Gold CartridgePure Gold CartridgeMercury Adsorption Cartridge
Quartz Glass 6 mm O.D. X 4 mm I.D.
Orifice(second seal)
Retention Groove(first seal)
NOTE: Cartridge Length 5 inches.
Pure Gold Matrix Assembly
Flow Direction
1 2 3
4 5
Mercury Adsorption Cartridge
Quartz Glass 6 mm O.D. X 4 mm I.D.
Orifice(second seal)
Retention Groove(first seal)
NOTE: Cartridge Length 5 inches.
Pure Gold Matrix Assembly
Flow Direction
1 2 3
4 5
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 12
Atomic FluorescenceAtomic FluorescenceMuch more sensitive than atomic adsorptionMuch more sensitive than atomic adsorption
MDL < 0.1 pg absoluteMDL < 0.1 pg absolute
Not subject to interferencesNot subject to interferences AA requires some sort of compensation/correction AA requires some sort of compensation/correction
schemescheme Interfering compounds (e.g. SOInterfering compounds (e.g. SO22, O, O33, organics) often , organics) often
present in concentrations present in concentrations thousandsthousands of times higher of times higher than Hgthan Hg
Inherently linearInherently linear Detector linear over >5 orders of magnitudeDetector linear over >5 orders of magnitude
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 13
Tekran AF Detector FeaturesTekran AF Detector Features
Most sensitive, most stable and lowest Most sensitive, most stable and lowest noise AF detector availablenoise AF detector available
Some reasons why:Some reasons why: Temperature controlled lamp blockTemperature controlled lamp block Optical feedback loop for constant lamp Optical feedback loop for constant lamp
intensityintensity Optical path purged with argon for stabilityOptical path purged with argon for stability
< 10 ml/min required for optical purge< 10 ml/min required for optical purge Magnetic shield on photomultiplier tubeMagnetic shield on photomultiplier tube
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 14
Tekran AF DetectorTekran AF Detector
Photomultiplier Tube
Interference Filter
Cuvette
Purge Gas Inlet
Lamp
Gasket
Lamp StabilizerCircuit BoardAssembly
Foam Insulation
Optical Feedback Sensor
Temperature Sensor
Heaters (x2)
LOWERBLOCK
UPPERBLOCK
PMTBLOCK
LAMPBLOCK
MagneticShield
Photomultiplier Tube
Interference Filter
Cuvette
Purge Gas Inlet
Lamp
Gasket
Lamp StabilizerCircuit BoardAssembly
Foam Insulation
Optical Feedback Sensor
Temperature Sensor
Heaters (x2)
LOWERBLOCK
UPPERBLOCK
PMTBLOCK
LAMPBLOCK
MagneticShield
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 15
Internal Permeation SourceInternal Permeation SourceAllows automated, unattended calibrationsAllows automated, unattended calibrations
Ensures that analyzer results are always accurateEnsures that analyzer results are always accurate
Allows standard additions to sample gasAllows standard additions to sample gas Ensures that analyzer is working properly even when Ensures that analyzer is working properly even when
confronted with difficult matricesconfronted with difficult matrices
Long life permeation tubeLong life permeation tube Low emission rate: Approx 30 Low emission rate: Approx 30 µµg/yrg/yr Theoretical life: thousands of years!Theoretical life: thousands of years!
Special auto-flush feature ensures no carryover Special auto-flush feature ensures no carryover after activationafter activation
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 16
Perm Source Flow DiagramPerm Source Flow Diagram
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 17
Integrates into Monitoring NetworksIntegrates into Monitoring Networks
Designed to look and operate like other Designed to look and operate like other continuous ambient air monitorscontinuous ambient air monitors Rack mountableRack mountable Easy to use interfaceEasy to use interface Two analog chart outputsTwo analog chart outputs Serial output provides hi-resolution results and:Serial output provides hi-resolution results and:
Instrument performance variablesInstrument performance variables Full record of each calibrationFull record of each calibration Record of instrument setup parametersRecord of instrument setup parameters
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 18
Operational CharacteristicsOperational Characteristics
Lamp lasts in excess of one year of Lamp lasts in excess of one year of continuous operationcontinuous operation Inexpensive, multi-sourcedInexpensive, multi-sourced Unlimited shelf lifeUnlimited shelf life No special isotopes requiredNo special isotopes required
NoNo zero drift ! zero drift ! Each reading is an integrated peak valueEach reading is an integrated peak value Detector drift does not affect resultsDetector drift does not affect results
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 19
Reporting BasisReporting Basis
Reports data readings based on sample Reports data readings based on sample volumes corrected to 0volumes corrected to 0°°C, 760 mmC, 760 mm All Hg concentrations in the literature are All Hg concentrations in the literature are
reported on this volume basisreported on this volume basis No reading-by-reading temperature and No reading-by-reading temperature and
pressure corrections required to normalize pressure corrections required to normalize datadata
Reporting at other conditions (e.g. 20 Reporting at other conditions (e.g. 20 °°C) is C) is possible simply by changing internal menu possible simply by changing internal menu settingsetting
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 20
True Ambient MeasurementTrue Ambient Measurement
Tekran Model 2537A is the Tekran Model 2537A is the only analyzer only analyzer availableavailable that is capable of accurately and that is capable of accurately and precisely measuring true ambient mercury precisely measuring true ambient mercury valuesvalues
Can measure mercury in Can measure mercury in actualactual gas gas matricesmatrices Virtually Virtually anyany analyzer (even uncompensated analyzer (even uncompensated
AA units) can give correct answers when AA units) can give correct answers when measuring mercury in zero air!measuring mercury in zero air!
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 21
Other ApplicationsOther Applications
With appropriate accessories and front ends With appropriate accessories and front ends the Tekran Model 2537A can perform:the Tekran Model 2537A can perform: Process gas monitoringProcess gas monitoring Continuous emissions monitoring (CEM)Continuous emissions monitoring (CEM) Mercury flux measurement Mercury flux measurement
Both chamber & gradient methods!Both chamber & gradient methods! Standard additionsStandard additions Speciation: ionic (reactive gaseous) mercurySpeciation: ionic (reactive gaseous) mercury Speciation: particulate bound mercurySpeciation: particulate bound mercury
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 22
Sample Data: Chlor-Alkali PlantSample Data: Chlor-Alkali Plant
6
4
2
N
EW
S
Concentrationsin ng/m3
Chlor-Alkali Plantlocated bearing 60º
distance 18 miles
Plot Duration: 60 daysData Interval: 15 min
WINDDIRECTION
vs.
MERCURY
0
Plot of wind direction vs. Plot of wind direction vs. ambient mercury valuesambient mercury values
Two months of continuous Two months of continuous monitoringmonitoring
Plant is located 18 miles Plant is located 18 miles distantdistant
Fish consumption Fish consumption advisories in effectadvisories in effect Fish levels were Fish levels were > 1.5 ppm> 1.5 ppm
even though air readings were even though air readings were only slightly elevatedonly slightly elevated
Global background:~1.5 ng/mGlobal background:~1.5 ng/m33
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 23
Depletions of Mercury in the ArcticDepletions of Mercury in the Arctic
The 2537A is capableThe 2537A is capable of extremely preciseof extremely precise measurement of even measurement of even sub-ambient readings. sub-ambient readings. In cases where two instruments are In cases where two instruments are running, they track each other very closely.running, they track each other very closely.
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 24
Validation of Depletion EventsValidation of Depletion Events
This line shows the % recovery of periodic automated This line shows the % recovery of periodic automated standard additions of elemental mercury to the sample standard additions of elemental mercury to the sample matrix. The recoveries are ~ 100%, yielding absolute matrix. The recoveries are ~ 100%, yielding absolute confidence that these unusual values represented a confidence that these unusual values represented a genuine, hitherto unknown phenomenon.genuine, hitherto unknown phenomenon.
Reactive Gaseous Reactive Gaseous Mercury MonitoringMercury Monitoring
Part 2Part 2
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 26
Tekran’s ObjectivesTekran’s Objectives
Development of an Development of an automated methodautomated method to to measure and differentiate different forms of measure and differentiate different forms of mercury in ambient airmercury in ambient air Reactive Gaseous Mercury (Reactive Gaseous Mercury (RGMRGM) ) Fine Fraction Particulate Mercury (Fine Fraction Particulate Mercury (HgHgPP)) Elemental mercury (Elemental mercury (HgHg00))
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 27
Why Ambient Air Mercury Speciation ?Why Ambient Air Mercury Speciation ?
Different forms of gaseous Hg have vastly Different forms of gaseous Hg have vastly different behaviors and environmental different behaviors and environmental impactsimpacts
Forms can interconvert in the atmosphere Forms can interconvert in the atmosphere and in various reservoirsand in various reservoirs
Classes of mercury in ambient air:Classes of mercury in ambient air: Elemental mercury: Elemental mercury: HgHg00,, GEM GEM Reactive mercury: Reactive mercury: HgHgIIII, , RGMRGM, , HgHg2+2+
Particulate mercury: Particulate mercury: HgHgPP, , TPMTPM
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 28
Elemental Mercury: HgElemental Mercury: Hg00
Typically 90+% of atmospheric Hg Typically 90+% of atmospheric Hg loadingsloadings
Relatively inert. Long residence timeRelatively inert. Long residence time
HgHg00 sources impact large areas sources impact large areas
Sources: chlor-alkali plants, gold and Hg Sources: chlor-alkali plants, gold and Hg mining, thermal power plantsmining, thermal power plants
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 29
Reactive Mercury: Hg(II) or RGMReactive Mercury: Hg(II) or RGMConsists of ionic, water soluble forms, Consists of ionic, water soluble forms,
primarily HgClprimarily HgCl22Usually only a few percent of total gaseous Usually only a few percent of total gaseous
mercury present in the atmospheremercury present in the atmosphereShort range: deposits relatively close to the Short range: deposits relatively close to the
source of emissionsource of emissionPrimary sources: Coal burning power plants, Primary sources: Coal burning power plants,
waste incinerators, chlor-alkali plantswaste incinerators, chlor-alkali plants
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 30
Difficulties Measuring RGMDifficulties Measuring RGMMethod must be Method must be 1-2 orders of magnitude1-2 orders of magnitude
more sensitivemore sensitive than total mercury methods than total mercury methods
Reject much larger Reject much larger elementalelemental component component
Must exclude Must exclude particulateparticulate bound mercury, bound mercury, however, conventional particulate filters however, conventional particulate filters cannot pass cannot pass RGMRGM
Apparatus must pass Apparatus must pass RGMRGM to the collector to the collector quantitatively. quantitatively. (RGM is extremely “sticky”)(RGM is extremely “sticky”)
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 31
Model 1130 - Principles of OperationModel 1130 - Principles of Operation
Patented by Tekran. Patented by Tekran. (US 6,475,802)(US 6,475,802)
Quartz, KCl coated annular denuder is Quartz, KCl coated annular denuder is thermally desorbed and regeneratedthermally desorbed and regenerated
Sampling PhaseSampling Phase Absorbs RGM while passing all elemental HgAbsorbs RGM while passing all elemental Hg Model 2537A reads Model 2537A reads HgHg00 during this phase during this phase
Desorption/Analysis PhaseDesorption/Analysis Phase Zero air used as carrierZero air used as carrier RGM released as RGM released as elementalelemental mercury mercury
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 32
RGM Sampling PhaseRGM Sampling PhaseDenuder is slightly warmDenuder is slightly warm
Inlet slightly warmInlet slightly warm
Denuder captures all Denuder captures all RGM while passing HgRGM while passing Hg00
Total sample flow is Total sample flow is 10 10 lpmlpm
Analyzer measures HgAnalyzer measures Hg00 during this timeduring this time
ZeroAir
SamplePump
MERCURY VAPOUR ANALYZER 2537A
AnnularDenuder
InletHeater
9 lpm 1 lpm
off
DenuderHeater
Ambient Air
OptionalModel 1135
Particulate Unit
Sampling Phase
Warm 50 ºC
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 33
Analysis PhaseAnalysis PhaseDenuder is heated to 500Denuder is heated to 500CC Inlet heated to clean up-Inlet heated to clean up-
stream glassware. (75 stream glassware. (75 C)C)Denuder releases captured Denuder releases captured
RGM as HgRGM as Hg00
Excess zero air flow and Excess zero air flow and heat cleans upstream heat cleans upstream componentscomponents
Instrument measures Instrument measures accumulated RGM as Hgaccumulated RGM as Hg00
ZeroAir
SamplePump
MERCURY VAPOUR ANALYZER 2537A
AnnularDenuder
InletHeater
off 1 lpm
6 lpm
DenuderHeater
ExcessZero Air
Heated 500 ºC
Desorption Phase
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 34
Quartz Denuder AssemblyQuartz Denuder Assembly
Elutriator JetElutriator Jet
ImpactorImpactor
Body & DiskBody & Disk
Zero AirZero Air
InletInlet
Sample AirSample Air
InletInlet
AnnulusAnnulus
ElbowElbow
(not used with 1135) (not used with 1135)
CouplerCouplerCouplerCoupler
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 35
Model 1130Model 1130 Speciation System Speciation System
Denuder ModuleDenuder Module (top) (top) Located out of doorsLocated out of doors Contains denuder element Contains denuder element
within high performance within high performance ovenoven
Impactor inlet removes Impactor inlet removes coarse particles (> 2.5 um)coarse particles (> 2.5 um)
Climate controlled enclosureClimate controlled enclosure
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 36
Model 1130Model 1130 Speciation System Speciation System
Pump ModulePump Module (bottom)(bottom) Located beside 2537ALocated beside 2537A Provides extra flow Provides extra flow
required during samplingrequired during sampling Generates the zero air Generates the zero air
required during desorptionrequired during desorption Also provides all zero air Also provides all zero air
required by Model 2537A!required by Model 2537A!
Heated lineHeated line (not shown)(not shown) 25 ft. length connects the two 25 ft. length connects the two
modulesmodules
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 37
Instrument CharacteristicsInstrument Characteristics
Fully automated, unattended operationFully automated, unattended operation Denuder exchanged every 1 or 2 weeks Denuder exchanged every 1 or 2 weeks
Operates in any environmentOperates in any environment Polar (Greenland, USA, Canada, Antarctica)Polar (Greenland, USA, Canada, Antarctica) Sub-tropical (Florida Everglades)Sub-tropical (Florida Everglades) Desert (Nevada)Desert (Nevada) Marine (ocean cruises)Marine (ocean cruises) High altitude (Mauna Loa)High altitude (Mauna Loa)
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 38
Data CharacteristicsData CharacteristicsHigh time resolution HgHigh time resolution Hg00 data provided during data provided during
sampling phase sampling phase Typically every 2½ or 5 minTypically every 2½ or 5 min Data is averaged to yield one HgData is averaged to yield one Hg00 point per sampling point per sampling
periodperiod
Single RGM integrated value every sample Single RGM integrated value every sample periodperiod Sample period: Sample period: 0.5 – 3 0.5 – 3 hourshours Analysis Period:Analysis Period: 25 – 60 25 – 60 minmin
Data values are for the Data values are for the exact sameexact same time period time period
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 39
Method ValidationMethod ValidationMethod was developed over a two year period at Method was developed over a two year period at
Tekran before being announcedTekran before being announced
Tested using both HgClTested using both HgCl22 and HgI and HgI22 as surrogates as surrogates
for RGMfor RGM
Two prototype units bought by State of FloridaTwo prototype units bought by State of Florida Units evaluated by Frontier Geosciences in Seattle Units evaluated by Frontier Geosciences in Seattle
under contract with Florida DEPunder contract with Florida DEP
Subsequent field testing by Keeler et al, Subsequent field testing by Keeler et al, University of Michigan & Lindberg et al., ORNLUniversity of Michigan & Lindberg et al., ORNL
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 40
Lab RGM Apparatus - (1997)Lab RGM Apparatus - (1997)
DenuderDenuderDenuderDenuder
ModelModel 2537A2537AModelModel 2537A2537A
CoffeeCoffee CanCanCoffeeCoffee CanCan
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 41
Preliminary Results - TorontoPreliminary Results - Toronto
RGM Comparison: SN:001, SN:002
May-23 12:00 May-24 00:00 May-24 12:00 May-25 00:00 May-25 12:00 May-26 00:00 May-26 12:00
1998
0
10
20
30
40
50
60
RG
M (
pg
/m3
)
RGM SN:001 (y)
RGM SN:002 (x)
SuccessiveDesorption (Blank Test)
Denuder Clean
Operation
Outdoor Air(Sampling through long inlet manifold)
Indoor Airy = 1.0595x - 0.5374
R2 = 0.9959
RGM Comparison: SN:001, SN:002
May-23 12:00 May-24 00:00 May-24 12:00 May-25 00:00 May-25 12:00 May-26 00:00 May-26 12:00
1998
0
10
20
30
40
50
60
RG
M (
pg
/m3
)
RGM SN:001 (y)
RGM SN:002 (x)
SuccessiveDesorption (Blank Test)
Denuder Clean
Operation
Outdoor Air(Sampling through long inlet manifold)
Indoor Airy = 1.0595x - 0.5374
R2 = 0.9959
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 42
Preliminary Results - TorontoPreliminary Results - TorontoElemental Mercury: SN:001 & SN:002
0
2
4
6
8
10
12
14
16
18
May-23 12:00 May-24 00:00 May-24 12:00 May-25 00:00 May-25 12:00 May-26 00:00 May-26 12:00
Date
Hg0 (
ng
/m3 )
Hg0 SN:001Hg0 SN:002
Outdoor Air
Indoor Air
Elemental Mercury: SN:001 & SN:002
0
2
4
6
8
10
12
14
16
18
May-23 12:00 May-24 00:00 May-24 12:00 May-25 00:00 May-25 12:00 May-26 00:00 May-26 12:00
Date
Hg0 (
ng
/m3 )
Hg0 SN:001Hg0 SN:002
Outdoor Air
Indoor Air
Two curves have been Two curves have been shifted horizontally for shifted horizontally for visibilityvisibility
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 43
Lab Testing: Frontier GeosciencesLab Testing: Frontier Geosciences
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Seattle RGM DataSeattle RGM DataAmbient Air Hg(0) and RGM in Downtown Seattle
0
2
4
6
8
10
12
:30
00
:30
12
:30
00
:30
12
:30
00
:30
12
:30
00
:30
12
:30
00
:30
12
:30
00
:30
12
:30
00
:30
12
:30
00
:30
12
:30
00
:30
12
:30
August 22-31, 1998
Hg
(0)
(ng
/m3)
0
50
100
150
200
250
300
350
RG
M (
pg
/m3)
Hg(0) Tek-043 RGM Tek-043
Courtesy: Frontier GeosciencesCourtesy: Frontier Geosciences
MunicipalMunicipalIncineratorIncineratorPlumePlume
MunicipalMunicipalIncineratorIncineratorPlumePlume
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 45
Mercury Levels - Rural MichiganMercury Levels - Rural Michigan
0
5
10
15
20
25
30
35
21:1
0
23:1
0
01:1
0
03:1
0
05:1
0
07:1
0
09:1
0
11:1
0
13:1
0
15:1
0
17:1
0
19:1
0
21:1
0
23:1
0
02:4
0
04:4
0
06:4
0
08:4
0
10:4
0
12:4
0
14:4
0
16:4
0
18:4
0
Time of Day (EDT)
RG
M (
pg
/m 3 )
.
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Hg
(0)
(ng
/m 3 )
.
Hg(II)Hg(0)
Dew Rain
27-Aug-98 29-Aug-9828-Aug-98
Courtesy: UMAQLCourtesy: UMAQL
Particulate Mercury Particulate Mercury MonitoringMonitoring
Part 3Part 3
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 47
Why Measure HgWhy Measure HgPP ? ?
Particulate bound mercury (Particulate bound mercury (TPMTPM / / HgHgPP) is ) is created directly by some industrial created directly by some industrial processes and also formed downwind of processes and also formed downwind of sources by the combination of mercury sources by the combination of mercury with existing particulateswith existing particulates
HgHgPP is removed even more rapidly via wet is removed even more rapidly via wet and dry deposition than is and dry deposition than is RGMRGM
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 48
Particulate Mercury: TPMParticulate Mercury: TPMConsists of various compounds of mercury Consists of various compounds of mercury
bound onto particlesbound onto particlesSize range: Generally thought to be < 3 umSize range: Generally thought to be < 3 umUsually only a few percent of total mercury Usually only a few percent of total mercury
present in the atmospherepresent in the atmosphereShort range: deposits relatively close to the Short range: deposits relatively close to the
source of emissionsource of emission
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 49
Difficulties Measuring HgDifficulties Measuring HgPP
Method must be 1-2 orders of magnitude more Method must be 1-2 orders of magnitude more sensitive than total mercury methodssensitive than total mercury methods
Must reject much larger Must reject much larger elementalelemental component component
Method must also exclude Method must also exclude reactive gaseous reactive gaseous mercury, however, normal particulate filters have mercury, however, normal particulate filters have problems in that they retain problems in that they retain somesome RGMRGM Virtually all conventional measurement methods have Virtually all conventional measurement methods have
recently been found to have serious analytical artifacts recently been found to have serious analytical artifacts due to RGM due to RGM (Landis, et al, ES&T, 2002)(Landis, et al, ES&T, 2002)
Artifact is non-quantitative and cannot be subtracted Artifact is non-quantitative and cannot be subtracted or correctedor corrected
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 50
Model 1135 - Principles of OperationModel 1135 - Principles of Operation
Sampling PhaseSampling Phase Sample passes through impactor to eliminate coarse Sample passes through impactor to eliminate coarse
particles (particles (> 2.5 um> 2.5 um)) Coated denuder captures RGM and eliminates RGM Coated denuder captures RGM and eliminates RGM
artifactartifact Quartz, Quartz, Regenerable Particulate FilterRegenerable Particulate Filter ( (RPFRPF) captures ) captures
fine fraction (fine fraction (< 2.5 um< 2.5 um) particulates) particulatesDesorption/Analysis PhaseDesorption/Analysis Phase
Zero air used as carrierZero air used as carrier Downstream Downstream pyrolyserpyrolyser is activated first is activated first RPF is then heated to desorb captured particulatesRPF is then heated to desorb captured particulates
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 51
RPFRPF Quartz wool captures bulk of Quartz wool captures bulk of
particulate matterparticulate matter
Quartz filter membrane Quartz filter membrane provides sharp cut-off (<0.1 provides sharp cut-off (<0.1 um)um)
Built in pyrolyzer section Built in pyrolyzer section converts desorbed species to converts desorbed species to HgHg00
Carbon based particulate Carbon based particulate matter on the filter is oxidized matter on the filter is oxidized to COto CO22 during desorption cycle during desorption cycle
Tail provides coolingTail provides cooling
Quartz WoolQuartz Wool
Quartz membrane filter diskQuartz membrane filter disk
PyrolyzerPyrolyzer
(quartz chips)(quartz chips)
Air GapAir Gap
Quartz WoolQuartz Wool
TailTail
InletInlet
(from denuder)(from denuder)
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 52
Model 1135 – Particulate Mercury MonitorModel 1135 – Particulate Mercury Monitor
Unit stacks on top of Model Unit stacks on top of Model 11301130
Allows Allows simultaneoussimultaneous deter- deter-mination of Hgmination of Hg00, RGM and , RGM and HgHgPP
Detection limit < 2 pg/mDetection limit < 2 pg/m33
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 53
Restrictor(100 ml/min)
MFM-1
CNCNO
ParticulateFilterPacks
Back PressureRegulator(1-5 PSI)
BufferTank
ZeroScrubber
V2
500
75 40
Fan
CaseHeater
Zero Air (to Denuder Module)
Control & StatusSignals
ZeroScrubber(1st stage)
INLET
AirInlet
Vent
Heater &Temperature
SensorLeads Zero
Inlet
SampleInlet
PUMP MODULE
MODEL 2537AANALYZER
SamplePump
Control Cable
(Heated)
HEATED LINE
Interchangeable inlets: Impactor for ambient air or'Tee' piece for manifold
V1
Rev 2.40
50
MFM
CONTROLLER
ZeroOut
SampleIn
DenuderModuleControl
cable
NC C
NO
ZEROAIR
SAMPLEFILTER
SodalimeTrap
Zero Filter(providedwith 2537A)
man_pics\1135flow.dsf
600 40600
OvenCooling Fan
FritFilter
Wool
Dimples
QuartzChips
Pyrolyzer
ParticulateFilter
Teflon Union (90º)Tail
QuartzWool
OvenExhaust
CaseExhaust
Fan
SampleLine
CaseHeater
PARTICULATEMODULE
ControlConnector
ControlCable
GL14-GL18 Union
Model 1135
RGMMODULE
Model 1130Model 1130
Fan Fan
CaseExhaust
OvenExhaust
(Shown in Sampling Mode)
OvenCooling Fan
Model 1130Model 1130& Model 1135 & Model 1135
Flow PathFlow Path
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 54
Ambient Air SpeciationAmbient Air Speciation
Mercury Species: Hg°, TPM & RGM St.Anicet (Quebec)
0.0
1.0
2.0
Jan-26 Jan-27 Jan-28 Jan-29 Jan-30 Jan-31 Feb-01 Feb-02
Ele
me
nta
l Me
rcu
ry -
ng
/m³
.
0
100
200
300
400
RG
M &
TP
M -
pg
/m³
.
Elemental Mercury - Hg°
Total Particulate Mercury - TPM
Reactive Gaseous Mercury - RGM
Model 1130 & Model 1135Model 1130 & Model 1135
Model 1130 - Reactive Gaseous Mercury (RGM)
Model 1135 - Total Particulate Mercury (TPM)
Model 2537A - Elemental Mercury (Hg0)
Model 1130 - Reactive Gaseous Mercury (RGM)
Model 1135 - Total Particulate Mercury (TPM)
Model 2537A - Elemental Mercury (Hg0)
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 55
Sample InstallationsSample Installations Figure 1 - Temporary
Model 1130/35 Installation (AES, Quebec Canada)
Figure 2 - Permanent Arctic Model 1130
Installation (NOAA, Barrow Alaska)
Figure 4 - Temporary Model 1130-P Installation (US EPA & Florida DEP)
Figure 3 - Model 1130-P (prototype) Mounted on roof of trailer
(US EPA, NERL)
Figure 5 - Model 1130-P sampling in Antarctica
(GKSS & AWI, Germany)
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 56
ConclusionConclusion
Measurement of mercury species at Measurement of mercury species at ambient levels is now practicalambient levels is now practical
Equipment has shown its utility and Equipment has shown its utility and reliability in a wide variety of sampling reliability in a wide variety of sampling situations around the worldsituations around the world
Some additional commitment in resources Some additional commitment in resources is required to implement a successful is required to implement a successful speciated mercury monitoring programspeciated mercury monitoring program
Automated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury SpeciationAutomated Mercury Speciationekran Inc. ekran Inc. 57
For More InformationFor More Information
Contact Contact [email protected]@tekran.com
Visit Visit www.tekran.comwww.tekran.com