Advances in science and applications of air pollution monitoring:A case study on oil sands monitoring

targeting ecosystem protectionJeffrey R. Brook

S G Cober, M Freemark, T Harner, SM Li, J Liggio, P Makar, B Pauli

Geographic perspective on the oil sands (OS)

Accumulation of organics, trace metals in snowpack• Surrounding ecosystems are potentially receiving a

large input in spring

Kelly et al. 2009. Oil sands development contributes polycyclic aromatic compounds to the Athabasca River and its tributaries. Proc. Natl. Acad. Sci. U.S.A.106(52):22346–22351

Accumulation of organics, trace metals in snowpack• While deposition drops off quickly with

distance, the OS are clearly implicated

Expert panel reviews (2010) of OS monitoring

Royal Society of Canada Panel: • regional and groundwater quality impacts on the Athabasca

River system were not a current threat to aquatic ecosystem viability

• concerns about the current monitoring program needed to be addressed

• minimal impacts by OS development projects on regional air quality, with the exception of odours, the amount of nitrogen oxide emissions, and the potential for regional acidification

The Royal Society of Canada. 2010. Environmental and Health Impacts of Canada’s Oil Sands Industry. https://rscsrc.ca/sites/default/files/RSC%20Oil%20Sands%20Panel%20Main%20Report%20Oct%202012.pdf

Expert panel reviews (2010) of OS monitoring

OS Advisory Panel:• many monitoring programs were unable to definitively

identify OS industrial impacts - not fully able to judge the absence of impacts

• deficiencies in sampling program design (including insufficient replication in space or time)

• lack of hypothesis-driven sampling regimes• ill-defined or undefined baseline conditions for inter-comparisons• inadequate analytical capabilities

Dowdeswell et al. 2010. A Foundation for the Future: Building an Environmental Monitoring System for the System for the Oil Sands. Gatineau: Environment Canada

Long-term record of atmospheric transport away from the OS operations• Lake sediment cores preserve history of atmospheric deposition

Kurek et al. 2013. Legacy of a half century of Athabasca oil sands development recorded by lake ecosystems. Proc. Natl. Acad. Sci. U.S.A. 110(5):1761-1766.

Long-term record of atmospheric transport away from the OS operations• Lake sediment cores preserve history of atmospheric deposition

Kurek et al. 2013. Legacy of a half century of Athabasca oil sands development recorded by lake ecosystems. Proc. Natl. Acad. Sci. U.S.A. 110(5):1761-1766.

Hebert C. 2019 The river runs through it: the Athabasca River delivers mercury to aquatic birds breeding far downstream. PLOS One

Increase in emissions detected from space

• Satellites have the resolution to isolate NOxemissions from growth in the southern and northern parts of the surface mining area

Satellite monitoring trends consistent with other measures of trends

• Due to limited number of surface sites possible, satellite can offer more complete picture of trends in total inputs to the atmosphere

Area-integrated mass

Column density of max

Average from surface monitoring sites

Bitumen production

McLinden et al. 2012. Air quality over the Canadian oil sands: A first assessment using satellite observations. Geophys. Res. Lett. 39(4)4804-

Overall region of potential impact seen from space • Multi-pollutant

index from satellite observations

• Includes NO2, SO2, PM2.5, NH3, HCHO, CO, light@night, O3objective analysis

Kharol et al. in preparation

OS Advisory Panel Recommendations

• A new program design is required to produce a first-class state-of-the-art monitoring system

• shared national vision and management framework• holistic and integrated • adaptive • scientifically credible• transparent and accessible

Dowdeswell et al. 2010. A Foundation for the Future: Building an Environmental Monitoring System for the System for the Oil Sands. Gatineau: Environment Canada

Joint Oil Sands Monitoring Program (JOSM)

• Respond to OS Advisory Panel recommendations• Develop in partnership with Alberta• Three main components: air; water; wildlife• Monitoring should assess and track long-term, cumulative

effects on ecosystems

Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring, 2012. http://www.ec.gc.ca/Scitech/D0AF1423-351C-4CBC-A990-4ADA543E7181/COM1519_Final%20OS%20Plan_02.pdf

Monitoring was well-developed by 2011

• Air, water, ecosystem monitoring was extensive

• A range of scientific questions were being explored

• Improvement possible• Additional questions to

explore

Challenges of assessing long-term ecosystem effects• uncertain whether single pollutant or stress or guidelines can be

sufficient for avoiding low dose effects and the effects of combinations of stressors

• limited thresholds or critical effect sizes (CES) for ecosystem safety • lack of information on toxicity thresholds based upon the levels of

chemicals measured within biota• nearly an inestimable chemical-space of potential metabolites and

degradates for the 1000s of parent compounds that are potentially released

Challenges of assessing long-term ecosystem effects• simple biological and chemical-physical indicators may not reflect

systems-based aspects of effect or Traditional Ecological Knowledge• chemical-physical indicators are easier to monitor but are only

correlates and not a measure of the actual biological response(s)• capacity to detect change in an organism is advancing rapidly, but

changes that affect an animal’s health or survival are not well-understood (i.e., meaningful change vs. trivial change)

• cellular or molecular markers may respond in a dose-dependent manner, with or without an apparent threshold

Challenges of assessing long-term ecosystem effects• uncertainties and data limitations with current critical loads and levels• high diversity in the level of nitrogen sensitivity (for eutrophication or

enhanced success) among ecosystems and species• metal critical loads can’t be calculated for locations where more

water is lost than gained and for soils with reducing conditions such as wetlands

Challenges of assessing long-term ecosystem effects• uncertainties and data limitations with current critical loads and levels• high diversity in the level of nitrogen sensitivity (for eutrophication or

enhanced success) among ecosystems and species• metal critical loads can’t be calculated for locations where more

water is lost than gained and for soils with reducing conditions such as wetlands

Unanswerable question?• Establish baselines• Develop tools

• Monitoring parameters and locations• Improved models• Sentinel species

Challenges of assessing long-term ecosystem effects• uncertainties and data limitations with current critical loads and levels• high diversity in the level of nitrogen sensitivity (for eutrophication or

enhanced success) among ecosystems and species• metal critical loads can’t be calculated for locations where more

water is lost than gained and for soils with reducing conditions such as wetlands

Unanswerable question?• Establish baselines• Develop tools

• Monitoring parameters and locations• Improved models• Sentinel species

Be Adaptive

The potential for impacts from acidic deposition• Upland forest soil and lake surveys

indicate that there are some sensitive ecosystems in the region

• Best model estimates are that critical loads are being exceeded

Source for CL map: https://www.canada.ca/en/environment-climate-change/services/air-pollution/publications/canada-united-states-air-quality-report-2014/chapter-2.html#s2-5-1.

Modelled exceedance of CLs

Critical loads of acidity for lakes or upland forest soils

Framework for developing the ECCC program

smog-related pollutants, acidifying compounds, volatile organic compounds (VOCs), metals, mercury and polycyclic aromatic compounds (PACs)

What is being emitted to the atmosphere ?

• VOCs and PM emissions are most uncertain

• Potential for large area and fugitive sources is high for these pollutants

Quantification of facility total emissions from aircraft flights

• Mass balance in and out of ‘box’ Gas Inlets Aerosol Inlet

Aerosol Probes

Gordon et al. 2015. Determining air pollutant emission rates based on mass balance using airborne measurement data over the Alberta oil sands operations. Atmos. Meas. Tech. 8:3745-3765, 2015. doi: 10.5194/amt-8-3745-2015

Transformation of emissions during transport

• Large amounts of secondary organic aerosols are formed

• Likely source is semi-volatile organic carbon emissions from exposed bitumen

• Multiple other species, some toxic, are also forming downwind

Liggio et al. 2016. Oil sands operations as a large source of secondary organic aerosols. Nature. 534(7605):91-94

Aircraft observations suggest VOC emissions are higher than current inventory values

• 11 of 93 species had aircraft-observed annualized emissions that were similar to reported values

• 82 species had lower reported emissions than aircraft-based emission estimates by a factor of 2 to 27,800

Li et al. 2017. Differences between Measured and Reported Volatile Organic Compound Emissions from Oil Sands Facilities in Alberta, Canada. Proc. Natl. Acad. Sci. U.S.A. 114(19):E3756-E3765

What do adjusted-emissions look like?

• Increased emissions spread over large areas where emissions are expected to occur

(a) di- and tri-substituted aromatics, (b) mono-substituted aromatics, (c) C4+ alkanes, (d) Primary organic particulate matter.

Stroud et al. 2018. Improving air quality model predictions of organic species using measurement-derived organic gaseous and particle emissions in a petrochemical-dominated region. Atmos. Chem. Phys. 18:13531-13545.

PM2.5 is dominated by larger particles

• 65–95% of PM2.5emissions are in the 1.28 to 2.56 μmdiameter range

• Larger than current inventory sizes

• Suggests fugitive-dust area sources

• new PM2.5 mass size distribution improved model prediction of PM2.5

Aircraft observations suggest PM2.5 emissions are higher than current inventory values

• A range of potential discrepancies observed

• Black carbon• CO2, CH4• PAHs• SO2 upset events

• New emissions estimates• Large particles (dust)• Trace toxics (HNCO, LMWOA)

Zhang et al. 2018 Emissions Preparation and Analysis for Multiscale Air Quality Modelling over the Athabasca Oil Sands Region of Alberta, Canada Atmos. Chem. Phys. 18, 10459–10481.

Tracking where emissions go is challenging

• Local atmospheric transport patterns are complex due to terrain and meteorological factors

• Will influence where the emissions deposit locally and further downwind

Photo by Andrea McNeil, Fort McKay First Nations

Models are necessary to provide insight into where emissions go and potential impacts• GEM-MACH was configured for

the highest resolution (2.5 km) routinely run in Canada

• Emissions inventory assessed and improved

• Several processes studied and improved

• Plume rise• Particle size distribution• SOA formation

• Sensitivity analyses for emission changes conducted

• SVOC/IVOC• VOCs• PM/base cations

Revisiting the question of acidic deposition was a key application for GEM-MACH• Best estimates to date; emissions and model improvements;• PLUS consideration of base cation neutralization (dust) and adjustment for

consistency with observed precipitation.

Total S Deposition (kg/ha/yr) Total N Deposition (kg/ha/yr) Total base cation Deposition (kg/ha/yr)

Makar et al. 2018 Estimates of exceedances of critical loads for acidifying deposition in Alberta and Saskatchewan. Atmos. Chem. Phys. 18:9897-9927.

Critical load exceedances

• More confidence that there is the potential for ecosystem impacts and in where they could occur

Terrestrial ecosystems Lake ecosystems

Satellite monitoring: An independent tool

Kharol et al. 2019 Decadal variation in nitrogen dioxide and sulfur dioxide dry deposition over North America from satellite measurements, in preparation for ACP.

Deposition of polycyclic aromatic compounds• Multi-year spring snow surveys also reflect the pattern reported by

Kelly et al. (2009) and add more detail to the areal extent and spatial distribution

Manzano et al. 2016. Temporal variation in the deposition of polycyclic aromatic compounds in snow in the Athabasca Oil Sands area of Alberta. Environ. Monit. Assess. 188(9):542.

OS sources of PACs

• Many point sources of reported emissions within the OS region

• Large areas with emissions expected and/or known

• Surface mining area• Tailings ponds

• Important non-OS sources

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Harner et al. 2018. Air Synthesis Review on Polycyclic Aromatic Compounds in the Oil Sands Region. Environ Rev. 26(4):430-468.

PACs are found in ecosystems

• Wood frog (tadpoles) were evaluated as a sentinel species

• PACs detected in tadpoles

• Semipermiable membrane devices are a potential non-invasive way to assess exposure and risk

• Decrease resembles snowpack results

Mundy et al. 2018. Using wood frog (Lithobates sylvaticus) tadpoles and semipermeable membrane devices to monitor polycyclic aromatic compounds in boreal wetlands in the oil sands region of northern Alberta, Canada. Chemosphere 214:148-157

Tree Swallow monitoring

• Chicks born and residing in locations closer to the OS operations have enhanced exposures to PACs

Fernie et al. 2018. Elevated exposure, uptake and accumulation of polycyclic aromatic hydrocarbons by nestling tree swallows (Tachycineta bicolor) through multiple exposure routes in active mining-related areas of the Athabasca oil sands region. Sci. Total Environ. 624:250–261.

Tree Swallow potential as a sentinel species

Criterion Tree Swallow RankLow Medium High

Robust and reproducible response ✔Research feasibility/tractability ✔Response sensitivity ✔Link to OS ✔Link to air pollution ✔Link to OS air pollution ✔Cost efficient ✔“Health-Based” measurements possible ✔Laboratory validation ✔Non-invasive or non-lethal possible ✔Regulatory relevance ✔“Threshold” measurements ✔Long-term monitoring capability ✔Power analysis for sample size possible ✔Human health linkage ✔Risk assessment/mapping possible ✔Indigenous knowledge incorporation possible

✔

Tracking water quality and aquatic effects

• An improved monitoring framework has been established

• Multiple focused studies

• Deposition• Concentration patterns

along tributaries• Toxicology• Conditions of multiple

aquatic species in relation to exposure gradients

PACs in aquatic systems

• PACs often below detection limits in bulk water samples

• PACs detected in fish (e.g. Slimy scuplin)

• Need a more-sensitive approach to monitor PACs in water

Parent PAHs – pink; Alkylated PAHs – green; total PAHs – blue

Culp et al. 2018. Synthesis Report for the Water Component, Canada-Alberta Joint Oil Sands Monitoring: Key Findings and Recommendations. Oil Sands Monitoring Program Technical Report Series No. 1.1, 46 p. ISBN 978-1-4601-4025-3.

• Multi-day exposures of SPMD provide sensitivity to study PACs

• Variations by location and season

• Distribution of compounds• Petrogenic vs. pyrogenic

PACs in aquatic systems

2013-15

Glozier et al. 2018, Surface Water Quality of the Athabasca, Peace and Slave Rivers and Riverine Waterbodies within the Peace-Athabasca Delta. Oil Sands Monitoring Program Technical Report Series No. 1.4. 64 p. ISBN: 978-1-4601-4152-6.

Deposition to snow of mercury and metals

• OS activities are a source of mercury

• Trace metals have a similar pattern

• Hg processes poorly understood

• Metal deposition (e.g., V, Ni, Zn) may be higher than what can be explained from current emission estimates

Kirk et al. 2014. Atmospheric Deposition of Mercury and Methylmercury to Landscapes and Waterbodies of the Athabasca Oil Sands Region. Environ. Sci. Technol. 48(13):7374-7383

Total Hg MeHg

Water quality sampling in key tributaries

• Significant increases in key metals (V, diss As, diss Se) from upstream to downstream of the OS development

• Development phases (e.g., land clearing) are associated with the largest increases

Alexander and Chambers 2016. Assessment of seven Canadian rivers in relation to stages in oil sands industrial development, 1972-2010. Environ. Rev. 24(4):484-494

Mercury in gull/tern eggs

• Survey across Alberta indicates higher levels in Athabasca region

Dolgova et al. 2018. Spatial trends in a biomagnifying contaminant: Application of amino acid compound–specific stable nitrogen isotope analysis to the interpretation of bird mercury levels. Environ. Toxicol. Chem. 37(5):1466–1475.

Year to year Hg variation in eggs

• Athabasca River is implicated as a source

• Time scale of movement and erosion processes, even including ice pack, play a role

• Not yet evidence that OS development or air emissions are the source of the Hg

Hebert 2019. The river runs through it: the Athabasca River delivers mercury to aquatic birds breeding far downstream. PLOS One 14(4)

Conclusions and Implications

• Quantification of atmospheric emissions for multiple pollutants needs to be improved

• reporting mechanisms and standards could be adapted to facilitate such improvements

• periodic validation is required where uncertainties are the largest

• With ongoing improvements, high resolution air quality prediction models represent an essential tool to future environmental assessments and cumulative environmental impact assessments

• Role of remote sensing needs to be considered

Conclusions and Implications

• Understanding of baseline conditions in the air, water and biota has improved significantly

• ongoing enhanced integrated monitoring, building on this progress, will help improve ecosystem protection measures in the oil sands region

• Sentinel species have been identified that could be used to identify and characterize potential impacts of wildlife exposure, both locally and regionally

Conclusions and Implications

• Best available estimates of S,N, acid deposition compared to critical loads to tell ecosystem effects my develop in some areas

• An integrated monitoring effort needs to be established that carefully assesses current acid deposition data and tracks change over time

• PACs are impacting aquatic and terrestrial wildlife at current concentration levels, but the significance of these impacts and long-term implications are not known

• attribution to emissions from oil sands development requires further assessment

Major Challenges

• A framework to evaluate the significance or implications of any observed effects, given the sensitivity of methods available, is needed

• There remains limited ability to attribute observed exposures and/or effects to OS air pollutant emissions given other sources and stressors

• Improved integration within disciplines and collaboration among different government departments and governments, and between industry and government and scientists

• Can common goals be established?