ALBERT

Description: Tropospheric ozone (O3) is a major component of photochemical smog and is a known human health hazard, as well as a damaging factor for vegetation. Its precursor compounds, nitrogen oxides (NOx) and volatile organic compounds (VOCs), have a variety of anthropogenic and biogenic sources and exhibit non-linear effects on ozone production. As an update to previous studies on ground-level ozone in the Greater Toronto Area (GTA), we present an analysis of NO2, VOC and O3 data from federal and provincial governmental monitoring sites in the GTA from 2000 to 2012. We show that, over the study period, summertime 24 h VOC reactivity and NO2 midday (11:00–15:00) concentrations at all sites decreased significantly; since 2000, all sites experienced a decrease in NO2 of 28–62% and in measured VOC reactivity of at least 53–71%. Comparing 2002–2003 to 2011–2012, the summed reactivity of OH towards NO2 and a suite of measured VOCs decreased from 8.6 to 4.6 s−1. Ratios of reactive VOC pairs indicate that the effective OH concentration experienced by primary pollutants in the GTA has increased significantly over the study period. Despite the continuous decrease in precursor levels, ozone concentrations are not following the same pattern at all stations; it was found that the Canada-wide Standard for ozone continues to be exceeded at all monitoring stations. Additionally, while the years 2008–2011 had consistently lower ozone levels than previous years, 2012 experienced one of the highest recorded summertime ozone concentrations and a large number of smog episodes. We demonstrate that these high ozone observations in 2012 may be a result of the number of days with high solar radiation, the number of stagnant periods and the transport of high ozone levels from upwind regions.

Description: Methane flux measurements were carried out at a temperate forest (Haliburton Forest and Wildlife Reserve) in central Ontario (45°17´11´´ N, 78°32´19´´ W) from June–October, 2011. Continuous measurements were made by an off-axis integrated cavity output spectrometer Fast Greenhouse Gas Analyzer (FGGA) from Los Gatos Research Inc. that measures methane (CH4) at 10 Hz sampling rates. Fluxes were calculated from the gas measurements in conjunction with wind data collected by a 3-D sonic anemometer using the eddy covariance (EC) method. Observed methane fluxes showed net uptake of CH4 over the measurement period with an average uptake flux (± standard deviation of the mean) of −2.7 ± 0.13 nmol m−2 s−1. Methane fluxes showed a seasonal progression with average rates of uptake increasing from June through September and remaining high in October. This pattern was consistent with a decreasing trend in soil moisture content at the monthly time scale. On the diurnal timescale, there was evidence of increased uptake during the day, when the mid-canopy wind speed was at a maximum. These patterns suggest that substrate supply of CH4 and oxygen to methanotrophs, and in certain cases hypoxic soil conditions supporting methanogenesis in low-slope areas, drive the observed variability in fluxes. A network of soil static chambers used at the tower site showed close agreement with the eddy covariance flux measurements. This suggests that soil-level microbial processes, and not abiological leaf-level CH4 production, drive overall CH4 dynamics in temperate forest ecosystems such as Haliburton Forest.

Description: Significant knowledge gaps persist in the understanding of forest–atmosphere exchange of reactive nitrogen oxides, partly due to a lack of direct observations. Chemical transport models require representations of dry deposition over a variety of land surface types, and the role of canopy exchange of NOx (= NO + NO2) is highly uncertain. Biosphere–atmosphere exchange of NOx and NOy (= NOx + HNO3 + PANs + RONO2 + pNO3− + ...) was measured by eddy covariance above a mixed hardwood forest in central Ontario (HFWR), and a mixed hardwood forest in northern lower Michigan (PROPHET) during the summers of 2011 and 2012 respectively. NOx and NOy mixing ratios were measured by a custom built two-channel analyzer based on chemiluminescence, with selective NO2 conversion via LED photolysis and NOy conversion via a hot molybdenum converter. Consideration of interferences from water and O3, and random uncertainty of the calculated fluxes are discussed. NOy flux observations were predominantly of deposition at both locations. The magnitude of deposition scaled with NOy mixing ratios, resulting in campaign-average deposition velocities close to 0.6 cm s−1 at both locations. A~period of highly polluted conditions (NOy concentrations up to 18 ppb) showed distinctly different flux characteristics than the rest of the campaign. Integrated daily average NOy flux was 0.14 mg (N) m−2 day−1 and 0.34 mg (N) m−2 day−1 at HFWR and PROPHET respectively. Concurrent wet deposition measurements were used to estimate the contributions of dry deposition to total reactive nitrogen oxide inputs, found to be 22% and 40% at HFWR and PROPHET, respectively.

Description: Tropospheric ozone (O3) is a major component of photochemical smog and is a known human health hazard as well as a damaging factor for vegetation. Its precursor compounds, nitrogen oxides (NOx) and volatile organic compounds (VOCs), have a variety of anthropogenic and biogenic sources and exhibit non-linear effects on ozone production. As an update to previous studies on ground-level ozone in the GTA, we present an analysis of NO2, VOC and O3 data from federal and provincial governmental monitoring sites in the GTA from 2000–2012. We show that over the study period, summertime 24 h VOC reactivity and NO2 midday (11:00–15:00) concentrations at all sites decreased significantly; since 2000, all sites experienced a decrease in NO2 of 28–62% and in measured VOC reactivity of at least 53–71%. Comparing 2002/2003 to 2011/2012, the summed reactivity of OH towards NO2 and a suite of measured VOCs decreased from 8.6 to 4.6 s−1. Ratios of reactive VOC pairs indicate that the effective OH concentration experienced by primary pollutants in the GTA has increased significantly over the study period. Despite the continuous decrease in precursor levels, ozone concentrations are not following the same pattern at all stations; it was found that the Canada-Wide Standard for ozone continues to be exceeded at all monitoring stations. Additionally, while the years 2008–2011 had consistently lower ozone levels than previous years, 2012 experienced one of the highest recorded summertime ozone concentrations and a large number of smog episodes. We demonstrate that these high ozone observations in 2012 may be a result of the number of days with high solar radiation, the number of stagnant periods and the transport of high ozone levels from upwind regions.

Description: Methane flux measurements were carried out at a temperate forest (Haliburton Forest and Wildlife Reserve) in central Ontario (45°17´11´´ N, 78°32´19´´ W) from June to October 2011. Continuous measurements were made by an off-axis integrated cavity output spectrometer that measures methane (CH4) at 10 Hz sampling rates. Fluxes were calculated from the gas measurements in conjunction with wind data collected by a 3-D sonic anemometer using the eddy covariance (EC) method. Observed methane fluxes showed net uptake of CH4 over the measurement period with an average uptake flux (±standard deviation of the mean) of −2.7 ± 0.13 nmol m−2 s−1. Methane fluxes showed a seasonal progression with average rates of uptake increasing from June through September and remaining high in October. This pattern was consistent with a decreasing trend in soil moisture content at the monthly timescale. On the diurnal timescale, there was evidence of increased uptake during the day, when the mid-canopy wind speed was at a maximum. These patterns suggest that substrate supply of CH4 to methanotrophs, and in certain cases hypoxic soil conditions supporting methanogenesis in low-slope areas, drives the observed variability in fluxes. A network of soil static chambers used at the tower site showed reasonable agreement with the seasonal trend and overall magnitude of the eddy covariance flux measurements. This suggests that soil-level microbial processes, and not abiological leaf-level CH4 production, drive overall CH4 dynamics in temperate forest ecosystems such as Haliburton Forest.

Description: Significant knowledge gaps persist in the understanding of forest–atmosphere exchange of reactive nitrogen oxides, partly due to a lack of direct observations. Chemical transport models require representations of dry deposition over a variety of land surface types, and the role of canopy exchange of NOx (= NO + NO2) is highly uncertain. Biosphere–atmosphere exchange of NOx and NOy (= NOx + HNO3 + PANs + RONO2 + pNO3− + ...) was measured by eddy covariance above a mixed hardwood forest in central Ontario (Haliburton Forest and Wildlife Reserve, or HFWR), and a mixed hardwood forest in northern lower Michigan (Program for Research on Oxidants: Photochemistry, Emissions and Transport, or PROPHET) during the summers of 2011 and 2012 respectively. NOx and NOy mixing ratios were measured by a custom-built two-channel analyser based on chemiluminescence, with selective NO2 conversion via LED photolysis and NOy conversion via a hot molybdenum converter. Consideration of interferences from water vapour and O3, and random uncertainty of the calculated fluxes are discussed. NOy flux observations were predominantly of deposition at both locations. In general, the magnitude of deposition scaled with NOy mixing ratios. Average midday (12:00–16:00) deposition velocities at HFWR and PROPHET were 0.20 ± 0.25 and 0.67 ± 1.24 cm s−1 respectively. Average nighttime (00:00–04:00) deposition velocities were 0.09 ± 0.25 cm s−1 and 0.08 ± 0.16 cm s−1 respectively. At HFWR, a period of highly polluted conditions (NOy concentrations up to 18 ppb) showed distinctly different flux characteristics than the rest of the campaign. Integrated daily average NOy flux was −0.14 mg (N) m−2 day−1 and −0.34 mg (N) m−2 day−1 (net deposition) at HFWR and PROPHET respectively. Concurrent wet deposition measurements were used to estimate the contributions of dry deposition to total reactive nitrogen oxide inputs, found to be 22 and 40% at HFWR and PROPHET respectively.