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


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


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


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


Model 2537A AnalyzerModel 2537A Analyzer


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


Flow Diagram of Model 2537A Flow Diagram of Model 2537A Mercury Analyzer Mercury Analyzer (Pat’d)(Pat’d)


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


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


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


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


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


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


Perm Source Flow DiagramPerm Source Flow Diagram


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


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


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


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!


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


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


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.


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


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))


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


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


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


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”)


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


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


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


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


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


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


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)


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


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


Lab RGM Apparatus - (1997)Lab RGM Apparatus - (1997)

DenuderDenuderDenuderDenuder

ModelModel 2537A2537AModelModel 2537A2537A

CoffeeCoffee CanCanCoffeeCoffee CanCan


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


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


Preliminary Results - TorontoPreliminary Results - TorontoElemental Mercury: SN:001 & SN:002

0

2

4

6

8

10

12

14

16

18


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


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


Lab Testing: Frontier GeosciencesLab Testing: Frontier Geosciences


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


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


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


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


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


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


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)


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


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


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)


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)


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


For More InformationFor More Information

Contact Contact [email protected]@tekran.com

Visit Visit www.tekran.comwww.tekran.com

introduction to model 1130/35 automated ambient air speciated mercury monitor f.h. schaedlich rev:...

Documents

quadrillion of mercury

mercury emissions

atomic adsorptionmdl

aat us epa

separate us

research triangle park

aa atomic absorption

international patentshas