2008 Progress Report: Using Carbohydrates as Molecular Markers to Determine the Contribution of Agricultural Soil to Ambient Fine and Course PM

EPA Grant Number: R832164
Title: Using Carbohydrates as Molecular Markers to Determine the Contribution of Agricultural Soil to Ambient Fine and Course PM
Investigators: Fraser, Matthew P.
Institution: Rice University
Current Institution: Arizona State University - Main Campus
EPA Project Officer: Chung, Serena
Project Period: December 1, 2004 through November 30, 2007 (Extended to November 30, 2010)
Project Period Covered by this Report: December 1, 2007 through November 30,2008
Project Amount: $441,299
RFA: Source Apportionment of Particulate Matter (2004) RFA Text |  Recipients Lists
Research Category: Particulate Matter , Air Quality and Air Toxics , Air

Objective:

The overall goal of the proposed project is to fully develop, employ and verify a technique to quantify the contribution of agricultural soils entrained in the atmosphere to ambient fine and coarse particulate matter (PM). This project will test the hypothesis that the carbohydrate species present in agricultural soils are chemically distinct from organic components in native soils as a result of soil improvements designed to raise the organic content and productivity of agricultural soil. This project will focus on comparison of the concentrations of marker species in agricultural soils to unimproved soils, and attempt to separate agricultural emissions from other fugitive dust sources (such as windblown dusts, unpaved road dusts or construction dusts).

Progress Summary:

Year 4 research focused on conducting air quality measurements of fine and coarse particulate matter in a new ecosystem in the desert Southwest.  The scientific motivation for this is to investigate the role of carbohydrates as markers for soil material in a different type of local environment from prior measurements in Texas.
 
Comparison of Texas and Arizona Saccharides:
In general, much lower saccharide concentrations were measured at the Arizona site than at the three Texas sites, due to a lower PM2.5 and the fraction of PM2.5 that is organic carbon, possibly as a result of the arid desert location. However, the average fraction of PM2.5 mass and OC that was quantified as saccharides at Higley (Az) was comparable to that measured at Dallas (Table 1), consistent with the fact that both sites are located in a metropolitan area, but in spite of the local climatic and ecological conditions. Among the three sampling sites in Texas, total measured saccharides were higher at the two rural sites (San Augustine and Clarksville) than the urban site, which is consistent with less contribution from biogenic sources at the urban location.
                    
Seasonal variations of saccharide compounds in PM2.5
Aerosol concentrations of individual saccharide compounds varied widely with the local season. Figure 1 shows the monthly variation of the measured major saccharide compounds. Of the measured saccharide compounds, levoglucosan was measured at the highest concentrations at all four sites, constituting more than half of the total measured saccharide concentrations in most of the samples. Levoglucosan levels were elevated in the first half of each sampling period, indicating the enhanced biomass burning activities in winter and early spring, which dropped in late spring and summer in both sampling regions.  The levoglucosan levels at the three sites in Texas also followed reports of the Texas-Oklahoma wildfires from November 2005 to April 2006, confirming the impact from biomass burning.  Glucose and sucrose were the second most abundant saccharide compounds, both of which had higher concentrations in spring. In particular, sucrose was dominant almost exclusively in March and April. Sucrose is an important sugar in developing flower buds and a known component of pollen grain, and the high aerosol sucrose in March and April suggested the origin of this compound from pollen or pollen fragment sources. Glucose is the simple sugar present in vascular plants and serves as a primary carbon reservoir for plants and microorganisms. Consistent with this role, the increase of glucose measured in aerosols during the growing season, was expected.  Another important sugar measured in all PM2.5 samples was trehalose, a primary saccharide serving as a stress protectant in bacteria, yeast, insects and a few higher plants. Trehalose measured in the Texas samples was elevated during the summer months (May, June and July), and a similar trend was observed for two major sugar polyols, mannitol and arabitol, an indication of the contribution from fungal spore derived sources. For the Arizona site, no samples were available after April to show the comparable trend, but trehalose was elevated throughout the sampling period from January to April. As these concentrations were equal or greater than trehalose measured at the three sites in Texas during the same period of the year while the concentrations of other fine aerosol saccharides measured in Arizona were much lower than those measured at the three Texan sites, this may suggest a unique influence from the desert environment and drought conditions on the metabolic activities of micro-organisms and plants in Arizona. 
 
PM10 vs. PM2.5 in Arizona aerosols
At the Arizona sampling site, we were able to compare saccharide concentrations in PM2.5 and PM10 samples collected simultaneously, with a goal of using the enrichment of individual saccharide compounds in fine and coarse particulate matter to elucidate local contributing sources.  While saccharide compounds were generally measured at higher concentrations in PM10 samples compared to parallel PM2.5 samples (Figure 2), two distinct patterns in this relationship were observed. Levoglucosan and glycerol had almost equivalent PM10 and PM2.5 concentrations while the remainder of the measured saccharide compounds (glucose, sucrose, trehalose, mannitol, arabitol, sorbitol, erythritol, ribitol and xylitol) had elevated PM10 relative to PM2.5 concentrations. These two different size fractionation patterns indicate that levoglucosan and glycerol predominately are associated with the fine fraction of PM while other saccharide compounds exist in both PM10 and PM2.5. This is consistent with levoglucosan being a tracer for wood smoke, with primary particle emissions in the submicron accumulation aerosol mode.  The other observed size fractionation shows glucose, sucrose, trehalose, mannitol and arabitol are mainly contributed from PBAPs, which have been reported to contribute mainly to coarse mode aerosols.
 
 
 
 
Table 1. Total measured saccharide concentrations, PM mass and organic carbon in PM2.5 samples at one suburban site (Higley) in Arizona, and two rural sites (San Augustine and Clarksville) and one urban site (Dallas) in Texas (n= total number of samples analyzed).
 
Higley, AZ
 (Jan - Apr 2008)
(n=45)
San Augustine, TX
(Nov 2005 - Jul 2006)
(n=76)
Clarksville, TX
(Jan - Jul 2006)
(n=40)
Dallas, TX
 (Jan - Jul 2006)
(n=57)
Total Measured Saccharide Concentration (ng/m3)
1.1 - 83.0
 (24.1)
15.4 - 355.1
 (70.4)
7.5 - 372.2
 (128.4)
15.8 - 196.0 (52.4)
PM2.5 Mass (ug/m3)
1.1 - 12.4 (5.9)
2.5 - 23.2 (9.9)
2.2 - 22.3 (10.2)
3.5 - 34.0 (11.2)
OC (ug/m3)
0.7 - 2.9 (1.6)
1.2 - 9.1 (2.6)
1.3 - 9.6 (3.2)
1.8 - 6.5 (3.2)
Total Saccharides/PM2.5 (%)
0.02 - 2.0 (0.5)
0.2 - 1.7 (0.8)
0.1 - 6.0 (1.6)
0.1 - 1.6 (0.6)
Total Saccharides/OC (%)
0.1 - 5.2 (1.5)
0.5 - 10.2 (3.3)
0.2 - 13.4 (5.2)
0.7 - 4.1 (2.0)
 
 

 
Figure 1. Seasonal variation of major saccharide compounds at one suburban site (Higley) in Arizona, and two rural sites (San Augustine and Clarksville) and one urban site (Dallas) in Texas (For each month, n~10 for San Augustine, Clarksville and Dallas, and n~15 for Higley, n=number of 24-hr sample analyzed.)
 
 
Figure 2. Average concentration of saccharide compounds measured in PM2.5 and PM10 from samples collected in Arizona (Total number of samples analyzed n=45 for PM2.5 and n=46 for PM10).
 

Future Activities:

We are continuing to analyze the data from the Higley field experiment with the goal of finishing the data interpretation and publication of results by November 2009 to conclude the project.

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Journal Articles:

No journal articles submitted with this report: View all 21 publications for this project

Supplemental Keywords:

agricultural emissions, source apportionment, molecular markers, soil carbohydrates, fine particulate matter, coarse particulate matter
 
, RFA, Scientific Discipline, Air, particulate matter, Environmental Chemistry, Environmental Monitoring, atmospheric particulate matter, chemical characteristics, airborne particulate matter, agricultural soils, molecular markers, PM, fine particulate formation

Progress and Final Reports:

Original Abstract
  • 2005 Progress Report
  • 2006 Progress Report
  • 2007 Progress Report
  • 2009
  • Final Report