Pierrette Blanchard

Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres

Atmospheric oxidation of biogenic hydrocarbons, such as monoterpenes, is estimated to be a significant source of global aerosol. Whereas laboratory studies have established that photochemical oxidation of monoterpenes leads to aerosol formation, there are limited field studies detecting such oxidation products in ambient aerosols. Drawing on prior results of monoterpene product analysis under controlled smog chamber conditions, we have identified organic aerosol components attributable to monoterpene oxidation in two forest atmospheres, Kejimkujik National Park, Nova Scotia, Canada, and Big Bear, San Bernardino National Forest, California, U.S.A. The major identified aerosol products derived from α-pinene and β-pinene oxidation include pinic acid, pinonic acid, norpinonic acid and its isomers, hydroxy pinonaldehydes, and pinonaldehyde, concentrations of which in the aerosol phase are in the sub ng m^(−3) range. Identification of oxidation products in atmospheric aerosol samples serves as direct evidence for aerosol formation from monoterpenes under ambient conditions.

Spatial patterns and temporal trends in mercury concentrations, precipitation depths, and mercury wet deposition in the North American Great Lakes region, 2002-2008

Annual and weekly mercury (Hg) concentrations, precipitation depths, and Hg wet deposition in the Great Lakes region were analyzed by using data from 5 monitoring networks in the USA and Canada for a 2002-2008 study period. High-resolution maps of calculated annual data, 7-year mean data, and net interannual change for the study period were prepared to assess spatial patterns. Areas with 7-year mean annual Hg concentrations higher than the 12 ng per liter water-quality criterion were mapped in 4 states. Temporal trends in measured weekly data were determined statistically. Monitoring sites with significant 7-year trends in weekly Hg wet deposition were spatially separated and were not sites with trends in weekly Hg concentration. During 2002-2008, Hg wet deposition was found to be unchanged in the Great Lakes region and its subregions. Any small decreases in Hg concentration apparently were offset by increases in precipitation.

Assessment of modeled mercury dry deposition over the Great Lakes region

Three sets of model predicted values for speciated mercury concentrations and dry deposition fluxes over the Great Lakes region were assessed using field measurements and model intercomparisons. The model predicted values were produced by the Community Multiscale Air Quality Modeling System for the year 2002 (CMAQ2002) and for the year 2005 (CMAQ2005) and by the Global/Regional Atmospheric Heavy Metals Model for the year 2005 (GRAHM2005). Median values of the surface layer ambient concentration of gaseous elemental mercury (GEM) from all three models were generally within 30% of measurements. However, all three models overpredicted surface-layer concentrations of gaseous oxidized mercury (GOM) and particulate bound mercury (PBM) by a factor of 2-10 at the majority of the 15 monitoring locations. For dry deposition of GOM plus PBM, CMAQ2005 showed a clear gradient with the highest deposition in Pennsylvania and its surrounding areas while GRAHM2005 showed no such gradient in this region; however, GRAHM2005 had more hot spots than those of CMAQ2005. Predicted dry deposition of GOM plus PBM from these models should be treated as upper-end estimates over some land surfaces in this region based on the tendencies of all the models to overpredict GOM and PBM concentrations when compared to field measurements. Model predicted GEM dry deposition was found to be as important as GOM plus PBM dry deposition as a contributor to total dry deposition. Predicted total annual mercury dry deposition were mostly lower than 5 μg m(-2) to the surface of the Great lakes, between 5 and 15 μg m(-2) to the land surface north of the US/Canada border, and between 5 and 40 μg m(-2) to the land surface south of the US/Canada border. Predicted dry deposition from different models differed from each other by as much as a factor of 2 at regional scales and by a greater extent at local scales.

A comparison of data quality control protocols for atmospheric mercury speciation measurements

Significant advances in the measurement of atmospheric mercury species have been made in the past 10 years yet limited protocols on quality control (QC) and assurance on this data have been published in the literature. Recently, considerable work has been done to develop quality control and assurance programs within North America. Environment Canada and the National Atmospheric Deposition Network (NADP) independently developed programs, RDMQ™ and AMQC, respectively, to QC atmospheric mercury speciation data (including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated to particles (PHg)). These 2 programs were assessed by the criteria on which the data is QCed and comparability of the final data products. Results show that the criteria used to flag data compare well within the 4 tested sites and that the number of flags for each criterion is generally comparable. The QC programs were applied to 2 distinct data sets and the final QCed data was compared. From a mid-latitude site, the final data sets compare very well and showed there to be a 0.3, 8.6 and 15% difference in the mean GEM, RGM and PHg concentrations post QC of each program. It is recommended that either the RDMQ or the AMQC programs be employed for a typical mid-latitude site. When the QC programs were applied to highly variable data, the data do not compare as well for RGM and PHg. Results showed a 2.7, 27 and 33% difference in the mean GEM, RGM and PHg concentrations, respectively, post QC of each program. It is recommended that RDMQ be used for data that is highly variable with high RGM/PHg concentrations as it allows for more manual correction over the QCed data. This investigation of 2 QC programs produced comparable data and that either of these programs can be used as standard methods for the quality control of atmospheric mercury speciation data.

From the city to the Lake: loadings of PCBs, PBDEs, PAHs and PCMs from Toronto to Lake Ontario.

Loadings from Toronto, Canada to Lake Ontario were quantified and major sources and pathways were identified, with the goal of informing opportunities for loading reductions. The contaminants were polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs) and polycyclic musks (PCMs). Loadings were calculated from measured concentrations for three major pathways: atmospheric processes, tributary runoff, and wastewater treatment plant (WWTP) effluents. Although atmospheric deposition to the Great Lakes has received the greatest attention, this was the dominant loading pathway for PCBs only (17 ± 5.3 kg/y or 66% of total loadings). PCB loadings reflected elevated urban PCB air concentrations due to, predominantly, primary emissions. These loadings contribute to consumption advisories for nearshore fish. PBDE loadings to the lake, again from mainly primary emissions, were 48% (9.1 ± 1.3 kg/y) and 42% (8.0 ± 5.7 kg/y) via tributaries and WWTPs, respectively, consistent with emissions deposited and subsequently washed-off of urban surfaces and emissions to the sewage system. PAHs loadings of 1600 ± 280 kg/y (71%) from tributaries were strongly associated with vehicle transportation and impervious surfaces. PCM loadings were 83% (±140 kg/y) from WWTP final effluent, reflecting their use in personal care products. Opportunities for source reduction lie in reducing the current inventories of in-use PCBs and PBDE-containing products, reducing vehicle emissions of PAHs and use of PAHs in the transportation network (e.g., pavement sealants), and improving wastewater treatment technology.

Impact of Closing Canada’s Largest Point-Source of Mercury Emissions on Local Atmospheric Mercury Concentrations

The Flin Flon, Manitoba copper smelter was Canadas largest point source of mercury emissions until its closure in 2010 after ~80 years of operation. The objective of this study was to understand the variables controlling the local ground-level air mercury concentrations before and after this major point source reduction. Total gaseous mercury (TGM) in air, mercury in precipitation, and other ancillary meteorological and air quality parameters were measured pre- and postsmelter closure, and mercury speciation measurements in air were collected postclosure. The results showed that TGM was significantly elevated during the time period when the smelter operated (4.1 ± 3.7 ng m(-3)), decreased only 20% during the year following its closure, and remained ~2-fold above background levels. Similar trends were observed for mercury concentrations in precipitation. Several lines of evidence indicated that while smelter stack emissions would occasionally mix down to the surface resulting in large spikes in TGM concentrations (up to 61 ng m(-3)), the largest contributor to elevated TGM concentrations before and after smelter closure was from surface-air fluxes from mercury-enriched soils and/or tailings. These findings highlight the ability of legacy mercury, deposited to local landscapes over decades from industrial activities, to significantly affect local air concentrations via emissions/re-emissions.

Soil–Air Mercury Flux near a Large Industrial Emission Source before and after Closure (Flin Flon, Manitoba, Canada)

Prior to its closure, the base-metal smelter in Flin Flon, Manitoba, Canada was one of the North Americas largest mercury (Hg) emission sources. Our project objective was to understand the exchange of Hg between the soil and the air before and after the smelter closure. Field and laboratory Hg flux measurements were conducted to identify the controlling variables and used for spatial and temporal scaling. Study results showed that deposition from the smelter resulted in the surrounding soil being enriched in Hg (up to 99 μg g(-1)) as well as other metals. During the period of smelter operation, air concentrations were elevated (30 ± 19 ng m(-3)), and the soil was a net Hg sink (daily flux: -3.8 ng m(-2) h(-1)). Following the smelter closure, air Hg(0) concentrations were reduced, and the soils had large emissions (daily flux: 108 ng m(-2) h(-1)). The annual scaling of soil Hg emissions following the smelter closure indicated that the landscape impacted by smelter deposition emitted or re-emitted almost 100 kg per year. Elevated soil Hg concentrations and emissions are predicted to continue for hundreds of years before background concentrations are re-established. Overall, the results indicate that legacy Hg deposition will continue to cycle in the environment long after point-source reductions.

Regression modeling of gas‐particle partitioning of atmospheric oxidized mercury from temperature data

Models describing the partitioning of atmospheric oxidized mercury (Hg(II)) between the gas and fine particulate phases were developed as a function of temperature. The models were derived from regression analysis of the gas-particle partitioning parameters, defined by a partition coefficient (Kp) and Hg(II) fraction in fine particles (fPBM) and temperature data from 10 North American sites. The generalized model, log(1/Kp) = 12.69–3485.30(1/T) (R2 = 0.55; root-mean-square error (RMSE) of 1.06 m3/µg for Kp), predicted the observed average Kp at 7 of the 10 sites. Discrepancies between the predicted and observed average Kp were found at the sites impacted by large Hg sources because the model had not accounted for the different mercury speciation profile and aerosol compositions of different sources. Site-specific equations were also generated from average Kp and fPBM corresponding to temperature interval data. The site-specific models were more accurate than the generalized Kp model at predicting the observations at 9 of the 10 sites as indicated by RMSE of 0.22–0.5 m3/µg for Kp and 0.03–0.08 for fPBM. Both models reproduced the observed monthly average values, except for a peak in Hg(II) partitioning observed during summer at two locations. Weak correlations between the site-specific model Kp or fPBM and observations suggest the role of aerosol composition, aerosol water content, and relative humidity factors on Hg(II) partitioning. The use of local temperature data to parameterize Hg(II) partitioning in the proposed models potentially improves the estimation of mercury cycling in chemical transport models and elsewhere.