Atmospheric Mercury Monitoring in CanadaCARA Mercury Monitoring:EC-TorontoP. Blanchard, D. MacTavish, R. Tanabe, M. Berthiaume, B. Vet, L. Zhang, C. EckleyEC-Halifax:R. Tordon, J. Dalziel EC-Montreal:L. Poissant, M. PiloteEC-Edmonton:B. Wiens, R. Mintz, M. LapalmeEC-Vancouver:C. EckleyMcGill University:P. Ariya, D. DeedsUniversity of Alberta:V. St. Louis, J. Graydon

Collaborators:EC-Toronto:S. Steffen, P. Lee, T. SchertzUniversity of Toronto:B. Branfireun

Why is mercury a concern in Canada?

• Mercury is toxic to humans and biota at levels found in the Canadian environment

– Indigenous populations in several areas of the Arctic have blood mercury levels that exceed U.S. and Canadian established guidelines

– Mercury is causing reproductive problems in wildlife at sites in Canada• Mercury is the primary trigger of human fish consumption advisories in

Canada• Aboriginal peoples, especially those in the Arctic, are particularly vulnerable

to mercury exposure due to high consumption levels of fish and marine animals

• Mercury levels are increasing in the arctic environment and, thus, potentially increasing risk to arctic peoples and wildlife

• Mercury is readily transported long distances, hence, global emissions impact levels of mercury in Canada

• Foreign emissions of mercury are increasing in some areas of the globe• The role of climate change in exacerbating this risk is uncertain

What are the trends in Canadian anthropogenic emissions of mercury to air?

Mercury Emissions Trends (without open sources)

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nes)

All Other Sources

NPRI

Environment Canada, Pollution Data Branch

What are the recent trends in atmospheric levels of mercury in Canada?

10/15/2009 Page 4

a) Annual

1.2

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signif. increase regarding previous yearsignif. decrease regarding previous year

linear regression from daily averagesannual median

• Mercury concentrations in the Canadian atmosphere have decreased significantly (~10%) from 1997 to 2005.

• Decreases correspond with decreasing trends in mercury in precipitation as observed by co-located MDN stations.

Urban Affected Sites

Temme et al. (2007) Atmos. Env., 41, 135-153.

Emissions Map

Deposition Map

Landscape-based Risk Map

Ecological Risk Map

Predictive Modelling

Air

Watershed

Levels /Effects

Time

Trends

Canadian Clean Air Regulatory Agenda (CARA)

• Reduce emissions of SOx, NOx, VOCs, GHGs and Mercury.

• Regulation of industrial sectors

• Implementation requires research, monitoring, modelling and assessment.

• Timeline is 2007-2011.

• Total Gaseous Mercury (TGM) or Gaseous Elemental Mercury (GEM):

– In-situ continuous monitor, 5 min., ~1.5 ng/m3

• Mercury in precipitation: – precipitation collector, weekly sample, 5-15 ng/L.– US Mercury Deposition Network or sent to Canadian laboratory.– Methyl Mercury analyses at some sites.

• Mercury Speciation:– In-situ, research-grade system, 2-3 hours.– Gaseous Elemental Mercury– Particulate Mercury, pg/m3

– Reactive Gaseous Mercury (RGM) or Gaseous Oxidized Mercury (GOM), pg/m3

– Research into methodology improvements.

Atmospheric Mercury Measurements

Dastoor et al: Modelled Total Annual Mercury Deposition in Canada from Canadian Point Sources.

CAPMoN (GEM and/or Precip (MDN)) Speciation (GEM, RGM, pHg)Other GEM or Precip

• Historical site for GEM (CAPMoN), MDN (NADP- NS01)

• Speciation: Jan. 2009-

• Site audit August 2009 (Mark Olsen -USGS)

Eastern Canada: Kejimkujik National Park

Western Canada: near coal-fired power plants.

GEM: 2004-presentSpeciation (Genesee): 2008 to

present.

Hg

Hg

Hg

Hg

Dry deposition onto canopypHg, RGM, MeHg

Wet depositionHg(II), MeHg

Throughfall depositionHg(II), MeHg

Litterfall depositionHg(II), MeHg

PhotoreductionHg(II), MeHg

Stomatal uptakeHg(0)

Retention in the canopyHg(II), MeHg

Experimental Lakes Area Total Deposition: Vince St. Louis and Jenny Graydon (U. of Alberta)

The forest canopy can result in up to 8

times more Hg being deposited to the watershed than

to open areas

Dastoor et al: Modelled Mercury Deposition Across Canada (μg m-2 y-1).

R&D: Modelling Dry Deposition of Atmospheric Mercury

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U10m=6 m s-1

Unstable stratificationTwo scaling parameters α=10, β=10

(Zhang et al., 2003)

RG

M D

ry D

epos

ition

Vel

ocity

, cm

/s

Zhang et al. Atmospheric Environment, 2009

Gold Nanoparticle Microextraction of RGM:• Gold preconcentrates RGM

through adsorption and amalgamation

• Nanoparticles have high surface area, can be placed on portable fibers, filters and other surfaces.

• Microextraction exposes air stream to small quantity of nanoparticles

Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry used to detect mercury species.

R&D: New Methods for Mercury Speciation, Parisa Ariya et al. (McGill University)

Collaboration with NADP-MDN-AMNet

• CAPMoN sites part of MDN. Intercomparison sites.

• Canadian scientists participate in the development of SOP and QA/QC protocols used for both Canadian and US NADP-AMNet sites.

• Speciation data QC intercomparison:– Compare data quality control handling methods between

NADP program and EC’s RDMQ module. – Year-long data sets from sites have been exchanged

with NADP

WWW.MERCURY2011.ORG