Errors in coarse particulate matter mass concentrations and spatiotemporal characteristics when using subtraction estimation methods

In studies of coarse particulate matter (PM_10-2.5), mass concentrations are often estimated through the subtraction of PM_2.5 from collocated PM₁₀ tapered element oscillating microbalance (TEOM) measurements. Though all field instruments have yet to be updated, the Filter Dynamic Measurement System (FDMS) was introduced to account for the loss of semivolatile material from heated TEOM filters. To assess errors in PM_10-2.5 estimation when using the possible combinations of PM₁₀ and PM_2.5 TEOM units with and without FDMS, data from three monitoring sites of the Colorado Coarse Rural–Urban Sources and Health (CCRUSH) study were used to simulate four possible subtraction methods for estimating PM_10-2.5 mass concentrations. Assuming all mass is accounted for using collocated TEOMs with FDMS, the three other subtraction methods were assessed for biases in absolute mass concentration, temporal variability, spatial correlation, and homogeneity. Results show collocated units without FDMS closely estimate actual PM_10-2.5 mass and spatial characteristics due to the very low semivolatile PM_10-2.5 concentrations in Colorado. Estimation using either a PM_2.5 or PM₁₀ monitor without FDMS introduced absolute biases of 2.4 µg/m³ (25%) to –2.3 µg/m³ (–24%), respectively. Such errors are directly related to the unmeasured semivolatile mass and alter measures of spatiotemporal variability and homogeneity, all of which have implications for the regulatory and epidemiology communities concerned about PM_10-2.5. Two monitoring sites operated by the state of Colorado were considered for inclusion in the CCRUSH acute health effects study, but concentrations were biased due to sampling with an FDMS-equipped PM_2.5 TEOM and PM₁₀ TEOM not corrected for semivolatile mass loss. A regression-based model was developed for removing the error in these measurements by estimating the semivolatile concentration of PM_2.5 from total PM_2.5 concentrations. By estimating nonvolatile PM_2.5 concentrations from this relationship, PM_10-2.5 was calculated as the difference between nonvolatile PM₁₀ and PM_2.5 concentrations.

Implications: Errors in the estimation of PM_10-2.5 concentrations using subtraction methods were shown to be related to the unmeasured semivolatile mass when using certain combinations of TEOM instruments. For the northeastern Colorado region, the absolute bias associated with this error significantly affects mean and 95th percentile values, which would affect assessment of compliance if PM_10-2.5 is regulated in the future. Estimating PM_10-2.5 mass concentrations using nonvolatile mass concentrations from collocated PM₁₀ and PM_2.5 TEOM monitors closely estimates the total PM_10-2.5 mass concentrations. A corrective model that removes the described error was developed and applied to data from two sites in Denver.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Windsor, Ontario exposure assessment study: design and methods validation of personal, indoor, and outdoor air pollution monitoring

The Windsor, Ontario Exposure Assessment Study evaluated the contribution of ambient air pollutants to personal and indoor exposures of adults and asthmatic children living in Windsor, Ontario, Canada. In addition, the role of personal, indoor, and outdoor air pollution exposures upon asthmatic children's respiratory health was assessed. Several active and passive sampling methods were applied, or adapted, for personal, indoor, and outdoor residential monitoring of nitrogen dioxide, volatile organic compounds, particulate matter (PM; PM-2.5 pm [PM2.5] and < or =10 microm [PM10] in aerodynamic diameter), elemental carbon, ultrafine particles, ozone, air exchange rates, allergens in settled dust, and particulate-associated metals. Participants completed five consecutive days of monitoring during the winter and summer of 2005 and 2006. During 2006, in addition to undertaking the air pollution measurements, asthmatic children completed respiratory health measurements (including peak flow meter tests and exhaled breath condensate) and tracked respiratory symptoms in a diary. Extensive quality assurance and quality control steps were implemented, including the collocation of instruments at the National Air Pollution Surveillance site operated by Environment Canada and at the Michigan Department of Environmental Quality site in Allen Park, Detroit, MI. During field sampling, duplicate and blank samples were also completed and these data are reported. In total, 50 adults and 51 asthmatic children were recruited to participate, resulting in 922 participant days of data. When comparing the methods used in the study with standard reference methods, field blanks were low and bias was acceptable, with most methods being within 20% of reference methods. Duplicates were typically within less than 10% of each other, indicating that study results can be used with confidence. This paper covers study design, recruitment, methodology, time activity diary, surveys, and quality assurance and control results for the different methods used.     

Effectiveness of emission control technologies for auxiliary engines on ocean-going vessels

Large auxiliary engines operated on ocean-going vessels in transit and at berth impact the air quality of populated areas near ports. This paper presents new information on the comparison of emission ranges from three similar engines and the effectiveness of three control technologies: switching to cleaner burning fuels, operating in the low oxides of nitrogen (NOx) mode, and selective catalytic reduction (SCR). In-use measurements of gaseous (NOx, carbon monoxide [CO], carbon dioxide [CO2]) and fine particulate matter (PM2.5; total and speciated) emissions were made on three auxiliary engines on post-PanaMax class container vessels following the International Organization for Standardization-8178-1 protocol. The in-use NOx emissions for the MAN B&W 7L32/40 engine family vary from 15 to 21.1 g/kW-hr for heavy fuel oil and 8.9 to 19.6 g/kW-hr for marine distillate oil. Use of cleaner burning fuels resulted in NOx reductions ranging from 7 to 41% across different engines and a PM2.5 reduction of up to 83%. The NOx reductions are a consequence of fuel nitrogen content and engine operation; the PM2.5 reduction is attributed to the large reductions in the hydrated sulfate and organic carbon (OC) fractions. As expected, operating in the low-NOx mode reduced NOx emissions by approximately 32% and nearly doubled elemental carbon (EC) emissions. However, PM2.5 emission factors were nearly unchanged because the EC emission factor is only approximately 5% of the total PM2.5 mass. SCR reduced the NOx emission factor to less than 2.4 g/kW-hr, but it increased the PM2.5 emissions by a factor of 1.5-3.8. This increase was a direct consequence of the conversion of sulfur dioxide to sulfate emissions on the SCR catalyst. The EC and OC fractions of PM2.5 reduced across the SCR unit.     

Cosolvent flushing for the remediation of PAHs from former manufactured gas plants

Cosolvent flushing is a technique that has been proposed for the removal of hydrophobic organic contaminants in the subsurface. Cosolvents have been shown to dramatically increase the solubility of such compounds compared to the aqueous solubility; however, limited data are available on the effectiveness of cosolvents for field-contaminated media. In this work, we examine cosolvent flushing for the removal of polycyclic aromatic hydrocarbons (PAHs) in soil from a former manufactured gas plant (FMGP). Batch studies confirmed that the relationship between the soil-cosolvent partitioning coefficient (K(i)) and the volume fraction of cosolvent (f(c)) followed a standard log-linear equation. Using methanol at an fc of 0.95, column studies were conducted at varying length scales, ranging from 11.9 to 110 cm. Removal of PAH compounds was determined as a function of pore volumes (PVs) of cosolvent flushed. Despite using a high f(c), rate and chromatographic effects were observed in all the columns. PAH effluent concentrations were modeled using a common two-site sorption model. Model fits were improved by using MeOH breakthrough curves to determine fitted dispersion coefficients. Fitted mass-transfer rates were two to three orders of magnitude lower than predicted values based on published data using artificially contaminated sands.     

Physical and chemical properties of feedlot pen surfaces located on moderately coarse- and moderately fine-textured soils in southern Alberta

Southern Alberta has the highest density of feedlot cattle in Canada, and there is a concern that leaching of water and contaminants may be greater for feedlots located on coarser-textured than finer-textured soils. Our objective was to determine if infiltration and leaching were greater for a 4-yr-old feedlot located on a moderately coarse-textured (MC) soil compared with two feedlots located on moderately fine-textured (MF) soils (5- and 52-yr-old pens). Various soil physical properties of feedlot pen surfaces were measured, including field-saturated hydraulic conductivity (K(fs)) and near-saturated hydraulic conductivity at -0.9 and -3.9 cm water potential. Selected chemical properties of feedlot soil layers were measured, as well as the chloride content of the soil profile (0-100 cm). Mean K(fs), K(-0.9), and K(-3.9) values were not significantly (P > 0.10) greater at the MC site than the two MF sites, indicating no evidence of greater infiltration on coarser-textured soils. In addition, mean K(fs), K(-0.9), and K(-3.9) values of soils within feedlot pens at all three sites were significantly (P < or = 0.10) reduced by 46 to 78% compared with soil outside the pens. Depth of chloride accumulation was greatest at the 52-yr-old feedlot on MF soil (60-70 cm), followed by 4-yr-old feedlot on MC soil (40-50 cm) and 5-yr-old feedlot on MF soil (30-40 cm). Visual inspection determined that the black interface layer formed within 2 mo of cattle stocking at all three sites.     

POTENTIAL EFFECTS OF CLIMATE CHANGE ON SURFACE‐WATER QUALITY IN NORTH AMERICA1

ABSTRACT: Data from long‐term ecosystem monitoring and research stations in North America and results of simulations made with interpretive models indicate that changes in climate (precipitation and temperature) can have a significant effect on the quality of surface waters. Changes in water quality during storms, snowmelt, and periods of elevated air temperature or drought can cause conditions that exceed thresholds of ecosystem tolerance and, thus, lead to water‐quality degradation. If warming and changes in available moisture occur, water‐quality changes will likely first occur during episodes of climate‐induced stress, and in ecosystems where the factors controlling water quality are sensitive to climate variability. Continued climate stress would increase the frequency with which ecosystem thresholds are exceeded and thus lead to chronic water‐quality changes. Management strategies in a warmer climate will therefore be needed that are based on local ecological thresholds rather than annual median condition. Changes in land use alter biological, physical, and chemical processes in watersheds and thus significantly alter the quality of adjacent surface waters; these direct human‐caused changes complicate the interpretation of water‐quality changes resulting from changes in climate, and can be both mitigated and exacerbated by climate change. A rigorous strategy for integrated, long‐term monitoring of the ecological and human factors that control water quality is necessary to differentiate between actual and perceived climate effects, and to track the effectiveness of our environmental policies.