Concentration and particle size of airborne toxic algae (brevetoxin) derived from ocean red tide events

Red tides in the Gulf of Mexico are formed by blooms of the dinoflagellate Karenia brevis, which produces brevetoxins (PbTx). Brevetoxins can be transferred from water to air in the wind-powered whitecapped waves during red tide episodes. Inhalation exposure to marine aerosol containing PbTx causes respiratory problems. A liquid chromatograph/ tandem mass spectrometric method was developed for the detection and quantitation of several PbTxs in ambient samples collected during red tide events. This method was complemented by a previously developed antibody assay that analyzes the entire class of PbTx compounds. The method showed good linearity, accuracy, and reproducibility, allowing quantitation of PbTx compounds in the 10 pg/m3 range. Air concentrations of PbTxs and brevenal for individual samples ranged from 0.01 to 80 ng/m3. The particle size showed a single mode with a mass median diameter between 6 and 10 microm, which was consistent for all of the PbTx species that were measured. Our results imply that individual PbTxs were from the same marine aerosol or from marine aerosol that was produced from the same process. The particle size indicated the likelihood of high deposition efficiency in the respiratory tract with the majority of aerosol deposited in the upper airways and small but not insignificant deposition in the lower airways.     

Measurements of size-segregated emission particles by a sampling system based on the cascade impactor

A special sampling system for measurements of size-segregated particles directly at the source of emission was designed and constructed. The central part of this system is a low-pressure cascade impactor with 10 collection stages for the size ranges between 15 nm and 16 microm. Its capability and suitability was proven by sampling particles atthe stack (100 degrees C) of a coal-fired power station in Slovenia. These measurements showed very reasonable results in comparison with a commercial cascade impactor for PM10 and PM2.5 and with a plane device for total suspended particulate matter (TSP). The best agreement with the measurements made by a commercial impactor was found for concentrations of TSP above 10 mg m(-3), i.e., the average PM2.5/PM10 ratios obtained by a commercial impactor and by our impactor were 0.78 and 0.80, respectively. Analysis of selected elements in size-segregated emission particles additionally confirmed the suitability of our system. The measurements showed that the mass size distributions were generally bimodal, with the most pronounced mass peak in the 1-2 microm size range. The first results of elemental mass size distributions showed some distinctive differences in comparison to the most common ambient anthropogenic sources (i.e., traffic emissions). For example, trace elements, like Pb, Cd, As, and V, typically related to traffic emissions, are usually more abundant in particles less than 1 microm in size, whereas in our specific case they were found at about 2 microm. Thus, these mass size distributions can be used as a signature of this source. Simultaneous measurements of size-segregated particles at the source and in the surrounding environment can therefore significantly increase the sensitivity of the contribution of a specific source to the actual ambient concentrations.     

Size-resolved source apportionment of airborne particle mass in a roadside environment

Airborne particulate hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs) were measured in six size fractions < 1.8 microm particle diameter at one site upwind and two sites downwind of the Interstate 5 freeway in San Diego, CA. The smallest size fraction collected was exclusively in the ultrafine size range (D(p) < 0.1 microm; PM0.1). Size distributions of hopanes, steranes, and PAHs peaked between 0.10-0.18 microm particle aerodynamic diameter with a tail extending into the PM0.1 size range. This pattern is similar to previous dynamometer studies of hopane, sterane, and PAH size distributions emitted from gasoline- and diesel-powered vehicles. Size-resolved source profiles were combined to form an "on-road" profile for motor oil, diesel, and gasoline contributions to EC and OC. The resulting equations were used to predict source contributions to the size distributions of EC and OC in the roadside environment. The method successfully accounted for the majority of the carbonaceous material in particles with diameter < 0.18 microm, with significant residual material in larger size fractions. The peak in both the measured and predicted EC size distribution occurred between 0.1-0.18 microm particle aerodynamic diameter. The predicted OC size distribution peaked between 0.1-0.18 microm particle diameter, butthe measured OC size distribution peaked between 0.56-1.0 microm particle diameter, possibly because of secondary organic aerosol formation. Predicted OC concentrations in particles with diameter < 0.18 microm were greater than measured values 18 m downwind of the roadway but showed good agreement 37 m downwind. The largest source contributions to the PM0.1 and PM0.18 size fractions were different. PM0.18 was dominated by diesel fuel and motor oil combustion products while PM0.1 was dominated by diesel fuel and gasoline fuel combustion products. Total source contributions to ultrafine (PM0.1) EC concentrations 37 m downwind of the roadway were 44 +/- 6% diesel fuel, 21 +/- 1% gasoline, 5 +/- 6% motor oil, and 30% unknown. Total source contributions to ultrafine (PM0.1) OC concentrations 37 m downwind of the roadway were 46 +/- 5% diesel fuel, 44 +/- 5% gasoline, 20 +/- 15% motor oil with a slight overprediction (11%). Diesel fuel appears to make the single largest contribution to ultrafine (PM0.1) particle mass given the fleet distribution during the current experiment.     

A field-based approach for deterimining ATOFMS instrument sensitities to ammonium and nitrate

Aerosol time-of-flight mass spectrometry (ATOFMS) instruments measure the size and chemical composition of individual particles in real-time. ATOFMS chemical composition measurements are difficult to quantify, largely because the instrument sensitivities to different chemical species in mixed ambient aerosols are unknown. In this paper, we develop a field-based approach for determining ATOFMS instrument sensitivities to ammonium and nitrate in size-segregated atmospheric aerosols, using tandem ATOFMS-impactor sampling. ATOFMS measurements are compared with collocated impactor measurements taken at Riverside, CA, in September 1996, August 1997, and October 1997. This is the first comparison of ion signal intensities from a single-particle instrument with quantitative measurements of atmospheric aerosol chemical composition. The comparison reveals that ATOFMS instrument sensitvities to both NH4+ and NO3- decline with increasing particle aerodynamic diameter over a 0.32-1.8 microm calibration range. The stability of this particle size dependence is tested overthe broad range of fine particle concentrations (PM1.8) = 17.6 +/- 2.0-127.8 +/- 1.8 microg m(-3)), ambient temperatures (23-35 degrees C), and relative humidity conditions (21-69%), encountered during the field experiments. This paper describes a potentially generalizable methodology for increasing the temporal and size resolution of atmospheric aerosol chemical composition measurements, using tandem ATOFMS-impactor sampling.     

Estimating ground-level PM2.5 in the eastern United States using satellite remote sensing

An empirical model based on the regression between daily PM2.5 (particles with aerodynamic diameters of less than 2.5 microm) concentrations and aerosol optical thickness (AOT) measurements from the multiangle imaging spectroradiometer (MISR) was developed and tested using data from the eastern United States during the period of 2001. Overall, the empirical model explained 48% of the variability in PM2.5 concentrations. The root-mean-square error of the model was 6.2 microg/m3 with a corresponding average PM2.5 concentration of 13.8 microg/m3. When PM2.5 concentrations greater than 40 microg/m3 were removed, model results were shown to be unbiased estimators of observations. Several factors, such as planetary boundary layer height, relative humidity, season, and other geographical attributes of monitoring sites, were found to influence the association between PM2.5 and AOT. The findings of this study illustrate the strong potential of satellite remote sensing in regional ambient air quality monitoring as an extension to ground networks. With the continual advancement of remote sensing technology and global data assimilation systems, AOT measurements derived from satellite remote sensors may provide a cost-effective approach as a supplemental source of information for determining ground-level particle concentrations.     

Hydroxycarboxylic acid-derived organosulfates: synthesis, stability, and quantification in ambient aerosol

Organosulfates have been proposed as contributors to aerosol growth and have been detected in both chamber and atmospheric aerosol samples. We present a simple method for the synthesis of quantitative analytical standards of two small hydroxycarboxylic acid-derived organosulfates, glycolic and lactic acid sulfate. Additionally, we discuss the stability of hydroxycarboxylic acid-derived organosulfates and their previously proposed sulfate hemiacetal isomers in commonly used solvents for filter extraction. The hydroxycarboxylic acid-derived organosulfates were found to be stable under acidic conditions comparable to those found in ambient aerosol. By using synthesized standards, quantitative organosulfate concentrations were measured from ambient particulate matter (PM(2.5)) collected in urban locations in the United States, Mexico City, and Pakistan. Lactic acid sulfate and glycolic acid sulfate concentrations ranged 0.4-3.8 ng/m(3) and 1.9-11.3 ng/m(3), respectively. We propose that glycolic acid sulfate represents an important tracer for atmospheric processes that form organosulfates in ambient particulate matter.     

Size distribution of particle-phase molecular markers during a severe winter pollution episode

Airborne particulate matter was collected using filter samplers and cascade impactors in six size fractions below 1.8 microm during a severe winter air pollution event at three sites in the Central Valley of California. The smallest size fraction analyzed was 0.056 < Dp <0.1 microm particle diameter, which accounts for the majority of the mass in the ultrafine (PM0.1) size range. Separate samples were collected during the daytime (10 a.m. to 6 p.m. PST) and nighttime (8 p.m. to 8 a.m. PST) to characterize diurnal patterns. Each sample was extracted with organic solvents and analyzed using gas chromatography mass spectrometry for molecular markers that can be used for size-resolved source apportionment calculations. Colocated impactor and filter measurements were highly correlated (R8 > 0.8) for retene, benzo[ghi]flouranthene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, perylene, indeno[1,2,3-cd]pyrene, benzo[ghi]perylene, coronene, MW302 polycyclic aromatic hydrocarbon (PAHs), 17beta(H)-21alpha(H)-30-norhopane, 17alpha(H)-21beta(H)-hopane, alphabetabeta-20R-C29-ethylcholestane, levoglucosan, and cholesterol. Of these compounds, levoglucosan was present in the highest concentration (60-2080 ng m(-3)) followed by cholesterol (6-35 ng m(-3)), PAHs (2-38 ng m(-3)), and hopanes and steranes (0-2 ng m(-3)). Nighttime concentrations were higher than daytime concentrations in all cases. Organic compound size distributions were generally similar to the total carbon size distributions during the nighttime but showed greater variability during the daytime. This may reflect the dominance of fresh emission in the stagnant surface layer during the evening hours and the presence of aged organic aerosol at the surface during the daytime when the atmosphere is better mixed. All of the measured organic compound particle size distributions had a single mode that peaked somewhere between 0.18 and 0.56 microm, but the width of each distribution varied by compound. Cholesterol generally had the broadest particle size distribution, while benzo[ghi]perylene and 17alpha(H)-21beta(H)-29-norhopane generally had sharper peaks. The difference between the size distributions of the various particle-phase organic compounds reflects the fact that these compounds exist in particles emitted from different sources. The results of the current study will prove useful for size-resolved source apportionment exercises.     

Concentration and dry deposition of mercury species in arid south central New Mexico (2001-2002)

This research was initiated to characterize atmospheric deposition of reactive gaseous mercury (RGM), particulate mercury (HgP; <2.5 microm), and gaseous elemental mercury (Hg0) in the arid lands of south central New Mexico. Two methods were field-tested to estimate dry deposition of three mercury species. A manual speciation sampling train consisting of a KCl-coated denuder, 2.5 microm quartz fiber filters, and gold-coated quartz traps and an ion-exchange membrane (as a passive surrogate surface) were deployed concurrently over 24-h intervals for an entire year. The mean 24-h atmospheric concentration for RGM was 6.8 pg m(-3) with an estimated deposition of 0.10 ng m(-2) h(-1). The estimated deposition of mercury to the passive surrogate surface was much greater (4.0 ng m(-2) h(-1)) but demonstrated a diurnal pattern with elevated deposition from late afternoon to late evening (1400-2200; 8.0 ng m(-2) h(-1)) and lowest deposition during the night just prior to sunrise (2200-0600; 1.7 ng m(-2) h(-1)). The mean 24-h atmospheric concentrations for HgP and Hg0 were 1.52 pg m(-3) and 1.59 ng m(-3), respectively. Diurnal patterns were observed for RGM with atmospheric levels lowest during the night prior to sunrise (3.8 pg m(-3)) and greater during the afternoon and early evening (8.9 pg m(-3)). Discernible diurnal patterns were not observed for either HgP or Hg0. The total dry deposition of Hg was 5.9 microg m-2 year-' with the contribution from the three species as follows: RGM (0.88 microg m(-2) year(-1)), HgP (0.025 microg m(-2) year(-1)), and Hg0 (5.0 microg m(-2) year(-1)). The annual wet deposition for total mercury throughout the same collection duration was 4.2 microg m(-2) year (-1), resulting in an estimated total deposition of 10.1 microg m(-2) year(-1) for Hg. On one sampling date, enhanced HgP (12 pg m(-3)) was observed due to emissions from a wildfire approximately 250 km to the east.     

Continuous fractionation of fly ash particles by SPUTT for the investigation of PCDD/Fs levels in different sizes of insoluble particles

A combined analytical method has been developed to characterize the size dependent levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) contained in fly ash particles from a municipal solid waste incinerator (MSWI). Gravitational SPLITT fractionation (GSF), a relatively new technique for the fast and continuous separation of micron sized particles, was used to fractionate a fly ash sample, directly collected from a bag-filter house of MSWI in Korea, into six different size groups (<1.0, 1.0-2.5, 2.5-5.0, 5.0-10, 10-20, and 20-53 microm in diameter) in water solution, and the resulting fractions are examined by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) in order to determine the concentration of PCDD/Fs according to these particle sizes. The results from SPLITT fractionation show that approximately 54% of the fly ash particles (sieved fraction <53 microm) by weight have been found to be smaller than 5.0 microm excluding the water soluble matter in the sample. From the HRGC/HRMS measurements, particle fractions in the size range of PM 1.0-2.5 and 2.5-5.0 appear to carry about 76 and 79 ng/g of PCDD/Fs which are relatively larger than those found in other diameter ranges. Principal component analysis (PCA) shows that particles larger than 5.0 microm are clustered into a group predominantly containing low chlorinated dioxins and fractions smaller than 5.0 microm into another group with lower chlorinated furans. This study demonstrated that the combining GSF with a secondary analytical method such as HRGC/HRMS has the potential to obtain size dependent information of particulate materials in relation to their production processes, chemical compositions, environmental fates, and other factors.     

Sterols and anionic surfactants in urban aerosol: emissions from wastewater treatment plants in relation to background concentrations

Aerosol particles that are emitted from aeration tanks of wastewater treatment plants (WWTPs) can be enriched with environmentally relevant wastewater constituents. In this study, aerosol particles were sampled simultaneously at the pre-aeration tank of a municipal WWTP and at two urban locations approximately 1 km away from the WWTP to evaluate the significance of these aerosol emissions. Moreover, aerosol particles were sampled at a small wastewater irrigation facility and at a rural site. In aerosol particles and wastewater, six sterols (cholesterol, coprostanol, campesterol, beta-sitosterol, stigmasterol, stigmastanol) and anionic surfactants (expressed in terms of methylene blue active substances, MBAS) were quantified. The results showed significantly higher concentrations of sterols and MBAS at the WWTP than atthe urban locations. At the WWTP, average concentrations of cholesterol (848 +/- 321 pg m(-3)), coprostanol (1132 +/- 565 pg m(-3)), and MBAS (132 +/- 43 ng m(-3)) in aerosol were approximately twice as high. This can be attributed to emissions from the treatment tank. Coprostanol, a unique tracer for wastewater, was detected only occasionally at the urban locations. The results of this study show that the aeration of wastewater is a continuously operating local source for organic compounds in aerosol. The wastewater irrigation facility was a minor source of aerosol-bound sterols (coprostanol, 287 +/- 218 pg m(-3)) and anionic surfactants (64 +/- 32 ng m(-3)). Except for coprostanol, all compounds were also present in samples of rural aerosol.     

Inhalation exposure to haloacetic acids and haloketones during showering

Inhalation exposure to haloacetic acids (HAAs) and haloketones (HKs) in contaminated drinking water occurs during showering. The size distribution of the aerosols generated by a shower was determined using an eight size-range particle counter, which measured particles from 0.1 to >2 microm. An exponential increase in aerosol numbers was observed while the shower water was on, while the aerosol numbers declined exponentially once the water was turned off. The half-lives of the shower aerosols were longer than 5 min after the shower water was turned off. Although the majority of the shower-generated aerosols were smaller than 0.3 microm, these aerosols only contributed approximately 2% to the measured total aerosol mass. The total shower-generated particulate HAA and HK concentrations collected on an open face filter were approximately 6.3 and 0.13 microg/m3, respectively, for shower water HAA and HK concentrations of 250 and 25 microg/L, respectively. The vapor-phase HK concentrations were 25-50 microg/m3. The estimate of the dose from inhalation exposure of disinfection byproducts (DBPs) in the particulate phase indicate that they represent less than 1% of the ingestion dose, so inhalation is not expected to be an important exposure route to nonvolatile water contaminants or the portion of volatile DBPs that stay in the particulate phase, unless the lung is the target organ. The vapor-phase levels of volatile HKs, though, are significantly higher and can contribute greater than 10% of the ingestion dose during a shower. Thus, risk assessment to the these DBPs needs to consider the inhalation route.     

Assessment of an aerosol treatment to improve air quality in a swine concentrated animal feeding operation (CAFO)

Poor air quality within swine concentrated animal feeding operations (CAFOs) poses a threat to workers, the surrounding community, and farm production. Accordingly, the current study was conducted to evaluate a technology for reducing air pollution including particulate matter (PM), viable bacteria, and ammonia within such a facility. The technology consists of an acid-oil-alcohol aerosol applied daily. Its effectiveness was evaluated by comparing air quality from before to after treatment and between treated and untreated sides of a barn separated by an impervious partition. On the untreated side, air quality was typical for a swine CAFO, with mean PM2.5 of 0.28 mg/m3 and PM(TOT) of 1.5 mg/m3. The treatment yielded a reduction in PM concentration of 75-90% from before to after treatment. Effectiveness increased with time, application, and particle size (40% reduction for 1 microm and 90% for >10 microm). Airborne bacteria levels (total bacteria, Enterobacteriaceae, and gram-positive cocci) decreased one logarithmic unit after treatment. In contrast, treatment had no effect on ammonia concentrations. These findings demonstrate the effectiveness of an intervention in yielding exposure and emission reductions.     

Simulated inhalation levels of fragrance materials in a surrogate air freshener formulation

This study measured postapplication exposure levels of fragrance materials in a surrogate air freshener formulation in an environmentally-controlled exposure room (ECER). A five-s spray was released to simulate normal consumer use conditions. Time-course airborne fragrance material levels were sampled with Tenax tubes, and aerosol size distributions were monitored with a TSI 3320 aerodynamic particle sizer. Triplicate experiments were performed for each of the control/test substances. The control substance (unfragranced formulation) experiments indicated that the airborne fragrance materials were not detected, suggesting that the base propellant formulation did not interfere with the sampling procedure or analytical results. The test substance experiments found that the higher the volatility of the fragrance material, the higherthe airborne fragrance concentration within the ECER. In the adult breathing zone height, the maximum concentrations of the nine fragrance materials ranged from 108 to 347 microg/m3 during the first minute postapplication. In the child breathing zone height, the maximum fragrance material concentrations ranged from 125 to 362 microg/m3 during 2-6 min postapplication. Particle size distributions indicated that approximately 60-70% of the generated aerosols were less than 1 microm aerodynamic diameter. Initial peak particle mass concentrations (<5 microm) were 800-1000 microg/m3 during the first minute postapplication. Following initial peak concentrations, there was approximately 10-15 min of fluctuation, and then particle levels decayed gradually and exponentiallyto near background levels. Exposure to the test formulation would originate from two components: particle-bound and vapor-phase fragrance materials. Particle-bound fragrance exposure accounted for approximately 47% and 72% of the total exposures during the first minute postapplication period in the adult and child breathing zone heights, respectively.     

Trimethylamine as precursor to secondary organic aerosol formation via nitrate radical reaction in the atmosphere

Amines in fine particulate matter have been detected and quantified during ambient studies of winter inversions in Logan, UT, using aerosol mass spectrometry. Amine-related compounds account for 0.5-6 microg m(-3) of fine particulate mass during some wintertime periods. The amine contributions sometimes show a clear diurnal pattern, reaching peak concentrations during the middle of the nightwhile decreasing during the morning and afternoon. Smog chamber reactions show that the reaction of tertiary amines with nitrate radical can account for this behavior in the atmosphere. The lower bound reaction rate of trimethylamine and nitrate radical is estimated at 4.4 x 10(-16) cm3/molecules/s with a conversion rate to the aerosol phase of approximately 65%. This suggests that amines could be a contributor to secondary organic aerosol formation in areas where nitrate radical is a significant player in oxidation chemistry.     

Temporal trends in atmospheric PM₂.₅, PM₁₀, elemental carbon, organic carbon, water-soluble organic carbon, and optical properties: impact of biomass burning emissions in the Indo-Gangetic Plain

The first simultaneous measurements and analytical data on atmospheric concentrations of PM(2.5), PM(10), inorganic constituents, carbonaceous species, and their optical properties (aerosol optical depth, AOD; absorption coefficient, b(abs); mass absorption efficiency, σ(abs); and single scattering albedo, SSA) from an urban site (Kanpur) in the Indo-Gangetic Plain are reported here. Significantly high aerosol mass concentration (>100 μg m(-3)) and AOD (> 0.3) are seen as a characteristic feature throughout the sampling period, from October 2008 to April 2009. The temporal variability in the mass fractions of carbonaceous species (EC, OC, and WSOC) is pronounced during October-January when emissions from biomass burning are dominant and OC is a major constituent (～30%) of PM(2.5) mass. The WSOC/OC ratio varies from 0.21 to 0.65, suggesting significant contribution from secondary organic aerosols (SOAs). The mass fraction of SO(4)(2-) in PM(2.5) (Av: 12.5%) exceeds that of NO(3)(-) and NH(4)(+). Aerosol absorption coefficient (@ 678 nm) decreases from 90 Mm(-1) (in December) to 20 Mm(-1) (in April), and a linear regression analysis of the data for b(abs) and EC (n = 54) provides a measure of the mass absorption efficiency of EC (9.6 m(2) g(-1)). In contrast, scattering coefficient (@ 678 nm) increases from 98 Mm(-1) (in January) to 1056 Mm(-1) (in April) and an average mass scattering efficiency of 3.0 ± 0.9 m(2) g(-1) is obtained for PM(10) samples. The highest b(scat) was associated with the dust storm event (April 17, 2009) over northern Iraq, eastern Syria, and southern Turkey; thus, resulting in high SSA (0.93 ± 0.02) during March-April compared to 0.82 ± 0.04 in October-February. These results have implications to large temporal variability in the atmospheric radiative forcing due to aerosols over northern India.     

Origins of primary and secondary organic aerosol in Atlanta: results of time-resolved measurements during the Atlanta Supersite Experiment

Time-resolved ambient particulate organic (OC) and elemental carbon (EC) data measured in Atlanta, GA, during the Atlanta Supersite Experiment (August3-September 1, 1999) were investigated to determine the temporal trends of atmospheric carbonaceous aerosol and to examine the relative contributions of primary and secondary OC to measured particulate OC. Mean 1-h average concentrations (ranges in parentheses) of PM2.5 OC, EC, and total carbon were 8.3 (3.6-15.8), 2.3 (0.3-9.6), and 10.6 (4.6-24.6) microg of C m(-3), respectively, based on Rutgers University/Oregon Graduate Institute in situ thermal-optical carbon analyzer measurements. Carbonaceous matter (organic material 40%; EC 8%) comprised approximately 48% of PM2.5 mass in Atlanta. Primary and secondary OC concentrations were estimated using an EC tracer method. Secondary OC contributed approximately 46% of measured particulate OC, and 1-h average contributions ranged up to 88%. Vehicle emissions appear to be the dominant contributors to measured EC and primary OC concentrations based on temporal patterns of EC, primary OC, and CO. This research suggests that secondary OC concentrations in Atlanta were influenced by (1) "fresh" secondary organic aerosol formed by photochemical reactions locally in the early afternoons as seen in the Los Angeles air basin and (2) "aged" secondary organic aerosol transported from upwind regions or formed on previous days. Nocturnal peaks in secondary OC and ozone concentrations were observed on several days. The most probable explanation for this is the favorable partitioning of semivolatile organic compounds to the particulate phase driven by temperature decreases and relative humidity increases at night and vertical transport of regional pollutants from above to ground level.     

Source apportionment of PM2.5 in the Southeastern United States using solvent-extractable organic compounds as tracers

A chemical mass balance (CMB) receptor model using particle-phase organic compounds as tracers is applied to apportion the primary source contributions to fine particulate matter and fine particulate organic carbon concentrations in the southeastern United States to determine the seasonal variability of these concentrations. Source contributions to particles with aerodynamic diameter < or =2.5 microm (PM2.5) collected from four urban and four rural/suburban sites in AL, FL, GA, and MS during April, July, and October 1999 and January 2000 are calculated and presented. Organic compounds in monthly composite samples at each site are identified and quantified by gas chromatography/mass spectrometry and are used as molecular markers in the CMB model. The major contributors to identified PM2.5 organic carbon concentrations at these sites in the southeastern United States include wood combustion (25-66%), diesel exhaust (14-30%), meat cooking (5-12%), and gasoline-powered motor vehicle exhaust (0-10%), as well as smaller but statistically significant contributions from natural gas combustion, paved road dust, and vegetative detritus. The primary sources determined in the present study when added to secondary aerosol formation account for on average 89% of PM2.5 mass concentrations, with the major contributors to PM2.5 mass as secondary sulfate (30+/-6%), wood combustion (15+/-12%), diesel exhaust (16+/-7%), secondary ammonium (8+/-2%), secondary nitrate (4+/-3%), meat cooking (3+/-2%), gasoline-powered motor vehicle exhaust (2+/-2%), and road dust (2+/-2%). Distinct seasonality is observed in source contributions, including higher contributions from wood combustion during the colder months of October and January. In addition, higher percentages of unexplained fine organic carbon concentrations are observed in July, which are likely due to an increase in secondary organic aerosol formation during the summer season.     

Emission rates and characterization of aerosols produced during the spreading of dewatered class B biosolids

This study measured aerosol emission rates produced during the spreading of dewatered class B biosolids onto agricultural land. Rates were determined in multiple independent experimental runs by characterizing both the source aerosol plume geometry and aerosol concentrations of PM10, total bacteria, heterotrophic plate count bacteria (HPC), two types of biosolids indicator bacteria, endotoxin, and airborne biosolids regulated metals. These components were also measured in the bulk biosolids to allow for correlating bulk biosolids concentrations with aerosol emission rates and to produce reconstructed aerosol concentrations. The average emission rates and associated standard deviation for biosolids PM10, total bacteria, HPC, total coliforms, sulfite-reducing Clostridia, endotoxin, and total biosolids regulated metals were 10.1 +/- 8.0 (mg/s), 1.98 +/- 1.41 x 10(9) (no./s), 9.0 +/- 11.2 x 10(7) (CFU/s), 4.9 +/- 2.2 x 10(3) (CFU/ s), 6.8 +/- 3.8 x 10(3) (CFU/s), 2.1 +/- 1.8 x 10(4) (EU/s), and 36.9 +/- 31.8 (microg/s) respectively. Based on the land application rates of spreaders used in this study, an estimated 7.6 +/- 6.3 mg of biosolids were aerosolized for every 1 kg (dry weight) applied to land. Scanning electron microscopy particle size distribution analysis of the aerosols revealed that greater than 99% of the emitted particles were less than 10 microm and particle size distributions had geometric mean diameters and standard deviations near 1.1 +/- 0.97 microm. The demonstrated correlations of bulk biosolids concentrations with aerosol emission rates, and the reconstruction of aerosol concentration based on PM10 and bulk biosolids concentration provide a more fundamental, bulk biosolids-based approach for extending biosolids aerosol exposure assessment to different land application scenarios and a broader range of toxins and pathogens.     

A case study of urban particle acidity and its influence on secondary organic aerosol

Size-resolved indicators of aerosol acidity, including H+ ion concentrations (H+Aer) and the ratio of stoichiometric neutralization are evaluated in submicrometer aerosols using highly time-resolved aerosol mass spectrometer (AMS) data from Pittsburgh. The pH and ionic strength within the aqueous particle phase are also estimated using the Aerosol Inorganics Model (AIM). Different mechanisms that contribute to the presence of acidic particles in Pittsburgh are discussed. The largest H+Aer loadings and lowest levels of stoichiometric neutralization were detected when PM1 loadings were high and dominated by SO4(2-). The average size distribution of H+Aer loading shows an accumulation mode at Dva approximately 600 nm and an enhanced smaller mode that centers at Dva approximately 200 nm and tails into smaller sizes. The acidity in the accumulation mode particles suggests that there is generally not enough gas-phase NH3 available on a regional scale to completely neutralize sulfate in Pittsburgh. The lack of stoichiometric neutralization in the 200 nm mode particles is likely caused by the relatively slow mixing of gas-phase NH3 into SO2-rich plumes containing younger particles. We examined the influence of particle acidity on secondary organic aerosol (SOA) formation by comparing the mass concentrations and size distributions of oxygenated organic aerosol (00A--surrogate for SOA in Pittsburgh) during periods when particles are, on average, acidic to those when particles are bulk neutralized. The average mass concentration of ODA during the acidic periods (3.1 +/- 1.7 microg m(-3)) is higher than that during the neutralized periods (2.5 +/- 1.3 microg m(-3)). Possible reasons for this enhancement include increased condensation of SOA species, acid-catalyzed SOA formation, and/or differences in air mass transport and history. However, even if the entire enhancement (approximately 0.6 microg m(-3)) can be attributed to acid catalysis, the upperbound increase of SOA mass in acidic particles is approximately 25%, an enhancement that is much more moderate than the multifold increases in SOA mass observed during some lab studies and inferred in SO2-rich industrial plumes. In addition, the mass spectra of OOA from these two periods are almost identical with no discernible increase in relative signal intensity at larger m/z's (>200 amu), suggesting that the chemical nature of SOA is similar during acidic and neutralized periods and that there is no significant enhancement of SOA oligomer formation during acidic particle periods in Pittsburgh.     

PBDEs in the atmosphere of three locations in western Europe

Atmospheric concentrations of PBDEs (108 samples in total) were measured at 2 rural/semirural sites in England and 1 remote site on the west coast of Ireland in the years 2001 and 2000, respectively. Detailed analysis of the factors affecting concentrations is performed. The United Kingdom (UK) has been a major producer and user of PBDEs. Concentrations of sigmaPBDEs at Mace Head (MH), Ireland ranged between 0.22 and 5.0 pg m(-3) with a mean of 2.6 pg m(-3) and were controlled primarily by advection. sigmaPBDEs concentrations at Hazelrigg (HR), northwest England, ranged between 2.8 and 37 pg m(-3) with a mean of 12 pg m(-3) and at Chilton (CH), southwest England between 3.4 and 33 pg m(-3) with a mean of 11 pg m(-3). The average mixture of PBDEs in air was similar to that of commercial penta-BDE products. Movement of air over local/regional sources influenced concentrations of PBDEs at all sites, particularly at MH. At the two English sites during the summer, concentrations of PBDEs were strongly influenced bytemperature, indicating that air-surface exchange processes play an important role. Advection became more influential during winter, particularly at CH, where a different congener profile was observed in some samples as ambient air temperatures decreased and PBDE concentrations increased. It is hypothesized that this was due to increased emissions from diffuse combustion sources.