Chemical mass balance source apportionment for combined PM2.5 measurements from U.S. non-urban and urban long-term networks

The Minnesota Particulate Matter 2.5 (PM_2.5) Source Apportionment Study was undertaken to explore the utility of PM_2.5 mass, element, ion, and carbon measurements from long-term speciation networks for pollution source attribution. Ambient monitoring data at eight sites across the state were retrieved from the archives of the Interagency Monitoring of Protected Visual Environments (IMPROVE) and the Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and analyzed by an Effective Variance – Chemical Mass Balance (EV-CMB) receptor model with region-specific geological source profiles developed in this study. PM_2.5 was apportioned into contributions of fugitive soil dust, calcium-rich dust, taconite (low grade iron ore) dust, road salt, motor vehicle exhaust, biomass burning, coal-fired utility, and secondary aerosol. Secondary sulfate and nitrate contributed strongly (49–71% of PM_2.5) across all sites and was dominant (≥60%) at IMPROVE sites. Vehicle exhausts accounted for 20–70% of the primary PM_2.5 contribution, largely exceeding the proportion in the primary PM_2.5 emission inventory. The diesel exhaust contribution was separable from the gasoline engine exhaust contribution at the STN sites. Higher detection limits for several marker elements in the STN resulted in non-detectable coal-fired boiler contributions which were detected in the IMPROVE data. Despite the different measured variables, analytical methods, and detection limits, EV-CMB results from a nearby IMPROVE-STN non-urban/urban sites showed similar contributions from regional sources – including fugitive dust and secondary aerosol. Seasonal variations of source contributions were examined and extreme PM_2.5 episodes were explained by both local and regional pollution events.     

Author’s Reply

A technique is developed to compute precision requirements for component parts of an emissions inventory to ensure (at a given confidence level) an overall acceptable precision in the estimate of total emissions. Since the emissions inventory is a basic requirement of air quality control implementation plans and provides a valuable management tool for planning air pollution control activities, it isi appropriate to state in quantitative terms the confidence that can be associated with each inventory. The approach reported here uses weighted sensitivity analysis methods to distribute both percentage and physical errors in source class emissions according to their contribution to the total emissions, and utilizes Chebyshev’s inequality to establish confidence levels for total emissions. The analysis has been extended to cover the case where one or more of the error components in a given inventory source class can be fixed by the analyst. The utility of the technique is manifold and several practical applications are reported. In particular, it serves to establish percentage error requirements for source categories to satisfy given error bounds for the overall emissions inventory at a given level of statistical confidence. The weighted sensitivity analysis technique possesses a high degree of generality, being applicable to compute component error requirements for any kind of data inventory which exhibits a hierarchical (tree-like) structure, as exemplified by NEDS Emissions Summary Reports. This work should be of interest to air pollution control planners at all levels of government and to anyone responsible for the air pollution portion of environmental impact statements.     

Evaluation of Regenerative-air Vacuum Street Sweeping on Geological Contributions to PM10

Street sweeping is often proposed as a means of reducing the emissions from paved roads. The objective of this study was to evaluate the effectiveness of street sweeping on ambient particulate matter concentrations and to determine the difference In source contributions to PM10 concentrations between street sweeping and non-street sweeping periods.

Chemically-speciated measurements of PM10 and PM2.5 were taken in the commercial section of Reno, Nevada, for a one-month sampling period. The Chemical Mass Balance (CMB) model was applied to these data and an average of approximately 50 percent of the PM10 was apportioned to resuspended geological material. During half of the sampling period, streets In the vicinity of the sampling site were completely swept with a regenerative-air vacuum sweeper, while no sweeping was performed during the remainder of the experiment. Ratios of primary geological contributions divided by primary motor vehicle contributions to PM10 were compared between sweeping and non-sweeping periods using analysis of variance. This ratio of source contributions minimizes the effects of variations in traffic volume and meteorological dispersion. No significant differences in geological contributions to PM10 were detected as a result of regenerative-air vacuum street sweeping.     

Black Carbon Aerosol at McMurdo Station,Antarctica

ABSTRACT

Aerosol light absorption as black carbon (BC) was measured from November 19, 1995, to February 6, 1996, at a location 0.65 km downwind of the center of McMurdo Station on the Antarctic coast. The results show a bimo-dal frequency distribution of BC concentrations. Approximately 65% of the measurements were found in a mode at a low range of concentrations centered at ~20 ng/m³. These concentrations are higher than those found at other remote Antarctic locations and probably represent contamination from the station. The remaining measurements were in a high-concentration mode (BC ~300 ng/m³), indicating direct impact of local emissions from combustion activities at the station. High values of BC were associated with winds from the direction of the station, and the BC flux showed a clear directionality. Maximum BC concentrations occurred between 7:00 and 11:00 a.m. The "polluted" mode accounted for more than 80% of the BC frequency-weighted impact at this location.     

Spatial Differences in Outdoor PM10 Mass and Aerosol Composition in Mexico City

Abstract

Twenty-five MiniVol samplers were operated throughout the Mexico City metropolitan region from February 22 through March 22, 1997, to evaluate the variability of PM₁₀ concentrations and composition. The highest PM₁₀ concentrations were found in neighborhoods with unpaved or dirty roads, and elements related to crustal material were the main cause of differences from nearby (<200 m) monitors that were not adjacent to the roadbed. SO₄ ^2?concentrations were homogeneous across the city. SO₄ ^2?measured at the city boundaries was about two-thirds of the concentrations measured within the urbanized area, indicating that most SO₄ ^2? is of regional origin. Elemental carbon (EC) and organic carbon (OC) concentrations were highly variable, with higher concentrations in areas that had high diesel traffic and older vehicles. Spatial correlations among PM₁₀ concentrations were high, even though absolute concentrations were variable, indicating a common effect of meteorology on the concentration or dispersion of local emissions.     

Limitations of an optimum sustainable population or potential biological removal approach for conserving marine mammals: Pacific walrus case study

Decision rules are the agreed-upon points at which specific management interventions are initiated. For marine mammal management under the U.S. Marine Mammal Protection Act (MMPA), decision rules are usually based on either a numeric population or biological-removal approach. However, for walrus and other ice-associated pinnipeds, the inability to reliably assess population numbers or biological removals highlights a significant gap in the MMPA, particularly when the Arctic environment is rapidly changing. We describe the MMPA's ecosystem-based management goals, and why managers have bypassed these goals in favor of an approach that depends upon numerical population assessment. We then revisit the statute's primary goals in light of current knowledge about the Pacific walrus ecosystem and new developments in environmental governance. We argue that to monitor and respond to changes in the walrus ecosystem, decision rules should be based on scientific criteria that depend less on the currently-impractical goal of accurately enumerating population size and trends, or removals from that population. Rather, managers should base decisions on ecological needs and observed ecological changes. To implement this approach would require an amendment to the MMPA that supports filling the gap in management with achievable decision rules. Alternatively, walrus and other ice-associated pinnipeds will remain largely unmanaged during a period of profound environmental change.     

How Green is Too Green? Public Opinion of What Constitutes Undesirable Algae Levels in Streams1

Abstract: A public opinion survey was carried out in Montana to ascertain if the public identifies a level of benthic (bottom‐attached) river and stream algae that is undesirable for recreation. The survey had two parts; an On‐River survey and a By‐Mail survey. The On‐River survey was conducted via 44 trips randomly scheduled throughout the state during which recreators were interviewed in‐person at the stream. Selection of stream segments and survey dates/times was based on known, statewide recreational use patterns. By‐Mail survey forms were sent to 2,000 individuals randomly selected from Montana’s Centralized Voter File (CVF) available from the Montana Secretary of State. The CVF was current through 2004 and represented over 85% of the state’s eligible voting population. In both surveys, eight randomly ordered photographs depicting varying levels of stream benthic algae were presented, and participants were asked if the algae level shown was desirable or undesirable for recreation. Survey form design, selection of photographs, and pretesting followed acceptable protocols that limited unintentional bias through survey execution. There were 433 returned forms (389 complete) for the By‐Mail survey, while the On‐River survey documented 563 interviews. In both surveys, as benthic algal chlorophyll a (Chl a) levels increased, desirability for recreation decreased. (Other measures of benthic algae biomass are presented as well.) For the public majority, mean benthic Chl a levels ≥200 mg/m² were determined to be undesirable for recreation, whereas mean levels ≤150 mg Chl a/m² were found to be desirable. Error rates were within the survey’s statistical design criteria (≤5%). The largest potential error source was nonresponse in the By‐Mail survey; however, the population represented by nonrespondents would have to exhibit profoundly different perceptions of river and stream algae to meaningfully alter the results. Results support earlier work in the literature suggesting 150 mg Chl a/m² represents a benthic algae nuisance threshold.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.