Ministry of the Environment, Conservation and Parks Mobile ... · Assessing non-compliance with O. Reg. 419/05 11 • Measurements of VOCs and other air toxics are compared with Ontario

Ministry of the Environment, Conservation and Parks

Mobile Monitoring and Passive Sampling of Volatile Organic Compounds Robert Healy

Background

• Emergency response - chemical spills and fires

• Industrial non-compliance field studies

• Focused community-scale air quality studies

• Development of new methodologies for measuring air pollutants

The Terrestrial Assessment and Field Services Unit (TAFSU)

2 Air and Odor Management Conference, Toronto, September 20 2019

Functions - Air:

• Part of the Environmental Monitoring and Reporting Branch

• Staff are a mix of environmental officers, scientists and technicians

Mobile Platforms

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• TAFSU deploys mobile monitoring platforms with complementary measurement capabilities for emergency response and assessing non-compliance by the regulated community

• The vehicles feature on-board generators, meteorological towers, data logging servers and air quality monitoring instrumentation

Air and Odor Management Conference, Toronto, September 20 2019

Mobile Platforms: Instrumentation

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TSQ truck

• Atmospheric pressure chemical ionization mass spectrometer (APCI-MS) for VOCs

• Particulate matter, sulphur dioxide, total reduced sulphur instrumentation


Mobile Platforms: Instrumentation

PTR truck

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• Proton transfer reaction mass spectrometer (PTR-MS) for VOCs

• Particulate matter, black carbon, nitrogen oxides instrumentation


Mobile Platforms: Mass Spectrometers

Complementary measurements of VOCs

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• PTR-MS well suited to real-time measurements of benzene, aromatic VOCs, chlorinated VOCs

• Switchable reagent ion source for measuring additional species including 1,3-butadiene

• APCI-MS targets polar VOCs including aldehydes, ketones, alcohols and amines


Emergency Response Activities

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• TAFSU responds to environmental emergencies involving emissions to air, including fires that may impact public health

• Measurements of air pollutants are compared with emergency screening values and the real-time results are provided to fire department staff at the scene

• The unit has responded to four emergencies in 2019 so far


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Wind direction

Mobile Monitoring: Source Identification


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Wind direction



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Assessing non-compliance with O. Reg. 419/05

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• Measurements of VOCs and other air toxics are compared with Ontario Regulation 419/05 standards and guidelines to assess whether concentrations downwind of a facility are within acceptable limits

• Measurement data need to be continuous and measured over a defined averaging period, for example 10 minutes, 1 hour or 24 hours depending on the standard

• Standards for VOCs are predominantly now based on 24 hour averaging periods, therefore mobile monitoring is less suitable for assessing non-compliance by industry

• A new method was required to enable continuous 24 hour measurement in the vicinity of industrial facilities in Ontario


Passive Monitoring of VOCs

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• Passive monitoring using sorbent packed tubes was recently introduced for monitoring benzene at refinery fencelines in the US using EPA Method 325

• Assessments of the performance of the passive tube method are relatively few and focused on US refinery sites, e.g. Texas

• Not representative of Ontario sampling conditions


Assessment of the Passive Tube Method

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• The thermal desorption tubes contain Carbopack X sorbent

• Method is calibrated by doping tubes using a gas dilution system

• Tubes are analyzed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS)

• For field sampling one end of the tube is fitted with a diffusion cap



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• Two separate six-week measurement campaigns (summer and winter) were undertaken at MECP’s roadside research station adjacent to Highway 401

• This section of highway is the busiest in North America, with >400,000 vehicles per day

• This traffic represents a continuous source of VOCs, including benzene, toluene, ethylbenzene and xylenes (BTEX)



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• Tubes were deployed for 24 hour and 14 day periods

• 24 hour canisters were also deployed and analyzed by ECCC

• Online GC systems were used to confirm BTEX concentrations


14-day Results


24-hour Results


Applications of Passive Sampling


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Wind direction

Mobile monitoring data



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Wind directionWind direction

Mobile monitoring data Passive tube data



Conclusions

• Mobile real-time air quality monitoring is essential for emergency response activities

• Mobile monitoring is also effective for identifying point sources of VOCs

• Passive sampling is relatively inexpensive, does not require power, and can be used to assess non-compliance with 24 hour standards

• Passive sampling is also well suited to long term community scale monitoring of VOCs for assessing chronic exposure

• The combination of mobile and passive monitoring of VOCs has proven to be a useful weight of evidence based approach to assessing non-compliance by the regulated community in Ontario


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[email protected]


Thanks to:

MECPJon WangNick KarellasGeorge RioualJulie BennettQingFeng ChenColman WongYemi SofowoteYushan SuLinda di FedericoTony Munoz Aaron ToddChris Charron

ECCCMay SiuSam BryantLuc WhiteDennis HerodJean-Pierre Charland

Appendix

24-hour Results: Temperature Dependence



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Benzene Toluene Ethylbenzene p-Xylene



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Benzene Toluene Ethylbenzene p-Xylene


Mobile Monitoring and Passive Sampling of Volatile Organic Compounds BackgroundMobile PlatformsMobile Platforms: InstrumentationMobile Platforms: InstrumentationMobile Platforms: Mass SpectrometersEmergency Response ActivitiesMobile Monitoring: Source IdentificationMobile Monitoring: Source IdentificationMobile Monitoring: Source IdentificationAssessing non-compliance with O. Reg. 419/05Passive Monitoring of VOCsAssessment of the Passive Tube MethodAssessment of the Passive Tube MethodAssessment of the Passive Tube Method14-day Results24-hour ResultsApplications of Passive SamplingApplications of Passive SamplingApplications of Passive SamplingConclusionsSlide Number 22Thanks to:Appendix24-hour Results: Temperature Dependence24-hour Results: Temperature Dependence24-hour Results: Temperature Dependence

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Ministry of the Environment, Conservation and Parks Mobile ... · Assessing non-compliance with O. Reg. 419/05 11 • Measurements of VOCs and other air toxics are compared with Ontario