Contribution of Nitrate and Carbonaceous Species to PM2.5 Observed in Canadian Cities

ABSTRACT

At a variety of Canadian monitoring sites, carbonaceous compounds were estimated to account for an average of 50% of fine particle mass. These estimates were determined by subtracting the total fine particle mass associated with inorganic compounds from the total fine mass determined gravimetrically. This approach, which yields an upper limit estimate of the total amount of carbon-related mass was necessary since particulate carbon was not measured in the Canadian National Air Pollution Surveillance (NAPS) network. In this paper, total carbon estimates are evaluated against organic and elemental carbon measurements at locations in the Greater Vancouver area and Toronto. In addition, particle nitrate measurements at seven Canadian locations are used to determine the importance of nitrate relative to total mass and to examine the sampling artifacts due to the loss of particle nitrate from Teflon filters used in the NAPS di-chotomous samplers.

Measurements of organic and elemental carbon indicated that the total carbon estimation approach provides representative estimates of the average contribution by carbonaceous material to the total fine and coarse mass. The average total carbon among all Vancouver area measurements (N = 225) was 4.28 μg m^-3, while the estimated value was 4.34 μg m^-3. There was a larger discrepancy between Toronto total carbon measurements (12.1 μg m^-3) and estimates (8.8 μg m^-3), which is attributed in part to sampling of particles above 10 mm in diameter. However, the R² relating the measurements and estimates was about 0.71 for both areas. Linear regression slopes of 0.98 for Vancouver and 0.78 for Toronto (nonsignificant intercepts) indicate little bias in the Vancouver estimates, but a tendency for underestimation as the observed total carbon concentration increased in Toronto.

Annually, nitrate was responsible for 17% and 12% of the fine mass in the Vancouver area and Ontario, respectively. In contrast, at two rural locations in southern Quebec and Nova Scotia, only 6% of fine mass was associated with nitrate. Due to filter losses, nitrate concentrations determined through the NAPS dichot sampling were much lower than actual concentrations (0.44 μg m^-3 vs. 2.63 μg m^-3). As a result of these losses (attributed mostly to loss during laboratory storage), previous total carbon estimates for the Canadian NAPS sites were likely to have been overestimated on average by about 10%.     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Ambient Air Benzene Concentrations in Canada (1989-1993): Seasonal and Day of Week Variations,Trends, and Source Influences

Abstract

Since 1987, the Pollution Measurement Division of the Environmental Protection Service, Environment Canada, has operated a field program for measuring benzene in ambient air. With the cooperation of provincial and municipal environmental agencies, samples have been collected at over 30 urban and rural monitoring sites across the country. Samples are collected in evacuated canisters and analyzed by gas chromatography with a mass-selective detector. Using data from all sites, the composite average benzene concentration for Canada over the years 1989 to 1993 was 3.6 μg/m³ and the composite median was found to be 2.6 μ/m³. Benzene concentrations are highest at urban sites near major streets and at sites influenced by industrial sources. For eighteen urban and suburban trend sites (those with no nearby industrial sources), composite annual median benzene concentrations decreased by 20% between 1989 and 1993. For the same period, median benzene concentrations decreased by 33% at four trend sites with nearby industries. At most monitoring sites the parameters for benzene and CO are highly correlated; supporting the inventory estimate that most emissions of benzene are due to vehicle exhaust. For sites with nearby industrial sources of benzene, the industries are estimated to account for 35 to 70% of the benzene dose experienced at the sites. These site specific contributions are much more significant than the estimated national emissions assigned to industrial sources.     

Database of PCDD/PCDF levels in ambient air and in samples related to the pulp and paper industry

A literature and questionnaire survey has been carried out in order that a database be developed for PCDD/PCDF levels in ambient air. The data received to date and entered into the database indicates that standardization in methodologies and reporting is required. The overall response to the survey, even with reminders, was disappointing.     

Inter-Laboratory Comparison of Air Particulate Monitoring Data

ABSTRACT

This paper compares three analytical methods that are often used to analyze composition of atmospheric aerosol: Ion Chromatography (IC), Proton Induced X-ray Emission (PIXE), and X-Ray Fluorescence (XRF). Three monitoring studies are discussed: (1) a comparison of air particulate data collected by several independent sampler/ analytical technique suites run by different laboratories; (2) a study involving two identical samplers and a single suite of analytical techniques; and (3) analysis of identical aerosol samples by two different techniques (XRF vs. PIXE). While the XRF versus PIXE project shows a very good agreement for most elements, the first interlaboratory study demonstrates the “real-life” noise introduced into the final data set by various sampling complications and different collection characteristics of the samplers used. The XRF versus PIXE study also revealed an unexplained deviation in measured sulphur concentrations for very lightly loaded samples. In the five-sampler comparison, two data sets provided by IC were approximately 20% lower than the three data sets obtained by PIXE and XRF. When two identical IMPROVE-compat-ible samplers were used and samples were subjected to similar procedures and the same analytical techniques, the variability between the two air concentration data sets significantly decreased.     

Temporal and spatial relationships in fine particle strong acidity, sulphate, PM1O, and PM2.5 across multiple canadian locations

The Canadian Acid Aerosol Measurement Program (CAAMP) was established in 1992 to gain a better understanding of the atmospheric behaviour of fine particle strong acidity (“acid aerosols”) and to facilitate an assessment of the potential health risks associated with acid aerosols and particles in general. During 1992. 1993 and 1994, annular denuder and filter measurements were taken at four sites in Ontario, two in Quebec, three in the Atlantic Provinces and one in the greater Vancouver area. Mean fine particle sulphate concentrations (SO₄²⁻) were highest in southern Ontario (annual average ranged from 40–70 nmol m⁻³), lowest at a site in the Vancouver area (average = 16 nmol m⁻³) and second lowest in rural Nova Scotia. However, mean fine particle strong acid concentrations (H⁺) were geographically different. The highest mean concentrations were at the east coast sites (annual average of up to 30 nmol m⁻³). Acidities were lower in areas where the fine particle acidity experienced greater neutralization from reaction with ammonia. This included the major urban centres (i.e. Toronto and Montréal) and areas with greater amounts of agricultural activity, as in rural southern Ontario. On average, ambient concentrations of fine and coarse particle mass were larger in the urban areas and also in areas where SO₄²⁻ levels were higher. All the particle components were episodic. However, compared to SO₄²⁻ and fine particles (PM_2.5 or PM_2.1, depending upon inlet design), episodes of H⁺ tended to be less frequent and of shorter duration, particularly in Ontario. Saint John, New Brunswick, had the highest mean annual H⁺ concentration, which was 30 nmol m⁻³. H⁺ episodes (24 h concentration > 100 nmol m⁻³) were also the most frequent at this location. The high levels in Saint John were partially due to local sulphur dioxide sources and heterogeneous chemistry occurring in fog, which, on average, led to a 50% enhancement in sulphate, relative to upwind conditions.There was a substantial amount of intersite correlation in the day to day variations in H⁺, SO₄²⁻ , PM_2.5 and PM₁₀ (fine + coarse particles) concentrations, which is due to the influence of synoptic-scale meteorology and the relatively long atmospheric lifetime of fine particles. Sulphate was the most regionally homogenous species. Pearson correlation coefficients comparing SO₄²⁻ between sites ranged from 0.6 to 0.9, depending on site separation and lag time. In many cases, particle episodes were observed to move across the entire eastern portion of Canada with about a two-day lag between the SO₄²⁻ levels in southern Ontario and in southern Nova Scotia.     

Adaptive management of marine mega-fauna in a changing climate

Management of marine mega-fauna in a changing climate is constrained by a series of uncertainties, often related to climate change projections, ecological responses, and the effectiveness of strategies in alleviating climate change impacts. Uncertainties can be reduced over time through adaptive management. Adaptive management is a framework for resource conservation that promotes iterative learning-based decision making. To successfully implement the adaptive management cycle, different steps (planning, designing, learning and adjusting) need to be systematically implemented to inform earlier steps in an iterative way. Despite the critical role that adaptive management is likely to play in addressing the impacts of climate change on marine mega-fauna few managers have successfully implemented an adaptive management approach. We discuss the approaches necessary to implement each step of an adaptive management cycle to manage marine mega-fauna in a changing climate, highlighting the steps that require further attention to fully implement the process. Examples of sharks and rays (Selachimorpha and Batoidea) on the Great Barrier Reef and little penguins, Eudyptula minor, in south-eastern Australia are used as case studies. We found that successful implementation of the full adaptive management cycle to marine mega-fauna needs managers and researchers to: (1) obtain a better understanding of the capacity of species to adapt to climate change to inform the planning step; (2) identify strategies to directly address impacts in the marine environment to inform the designing step; and (3) develop systematic evaluation and monitoring programs to inform the learning step. Further, legislation needs to flexible to allow for management to respond.     

Pollution,habitat loss,fishing, and climate change as critical threats to penguins

Cumulative human impacts across the world's oceans are considerable. We therefore examined a single model taxonomic group, the penguins (Spheniscidae), to explore how marine species and communities might be at risk of decline or extinction in the southern hemisphere. We sought to determine the most important threats to penguins and to suggest means to mitigate these threats. Our review has relevance to other taxonomic groups in the southern hemisphere and in northern latitudes, where human impacts are greater. Our review was based on an expert assessment and literature review of all 18 penguin species; 49 scientists contributed to the process. For each penguin species, we considered their range and distribution, population trends, and main anthropogenic threats over the past approximately 250 years. These threats were harvesting adults for oil, skin, and feathers and as bait for crab and rock lobster fisheries; harvesting of eggs; terrestrial habitat degradation; marine pollution; fisheries bycatch and resource competition; environmental variability and climate change; and toxic algal poisoning and disease. Habitat loss, pollution, and fishing, all factors humans can readily mitigate, remain the primary threats for penguin species. Their future resilience to further climate change impacts will almost certainly depend on addressing current threats to existing habitat degradation on land and at sea. We suggest protection of breeding habitat, linked to the designation of appropriately scaled marine reserves, including in the High Seas, will be critical for the future conservation of penguins. However, large‐scale conservation zones are not always practical or politically feasible and other ecosystem‐based management methods that include spatial zoning, bycatch mitigation, and robust harvest control must be developed to maintain marine biodiversity and ensure that ecosystem functioning is maintained across a variety of scales. Contaminación, Pérdida de Hábitat, Pesca y Cambio Climático como Amenazas Críticas para los Pingüinos     

Observations and Interpretations from the Canadian Fine Particle Monitoring Program

ABSTRACT

Canadian particle monitoring programs examining PM10, PM2.5, and particle composition have been in operation for over 10 years. Until recently, the measurements were manual/filter-based with 24-hr sample collection varying in frequency from daily to every sixth day, using GrasebyAnderson dichotomous samplers. In the past few years, these monitoring activities have been expanded to include hourly measurements using tapered element oscillating microbalances (TEOMs). This continuous monitoring program started operation focusing on PM_10, but now emphasizes PM_2.5 through the addition of more TEOMs and switching of the inlets of some of the existing units. The data from all of these measurement activities show that there are broad geographical differences and also local- to regional-scale spatial differences in mass and composition of PM2.5. Due to variations in sources, significantly different PM2.5 concentrations are not uncommon within the same city. Comparison of nearby urban and rural sites indicates that 30 and 40% of the PM_2.5 is from local urban sources in Montreal and Toronto, respectively. Hourly PM_2.5 measurements in Toronto suggest that vehicular emissions are an important contributor to urban PM_2.5. There has been a decreasing trend in urban PM_2.5, with annual average concentrations between the 1987–1990 and 1993–1995 periods decreasing by 11 to 39%, depending upon the site. The largest declines were in Montreal and Halifax, and the smallest decline was in Toronto. Comparison of 24-hr TEOM and manual dichotomous sampler PM_2.5 measurements from a site in Toronto indicates that the TEOM results in lower concentrations. The magnitude of this difference is relatively small in the warmer months, averaging about 12%. During the colder months the difference averages about 23%, but can be as large as 50%.