Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

Determination of Levoglucosan in Atmospheric Fine Particulate Matter

Abstract

A microanalytical method suitable for the quantitative determination of the sugar anhydride levoglucosan in low-volume samples of atmospheric fine particulate matter (PM) has been developed and validated. The method incorporates two sugar anhydrides as quality control standards. The recovery standard sedoheptulosan (2,7-anhydro-β-D-altro-heptulopyranose) in 20 μL solvent is added onto samples of the atmospheric fine PM and aged for 1 hr before ultrasonic extraction with ethylacetate/ triethylamine. The extract is reduced in volume, an internal standard is added (1,5-anhydro-D-mannitol), and a portion of the extract is derivatized with 10% by volume N-trimethylsilylimidazole. The derivatized extract is analyzed by gas chromatography/mass spectrometry (GC/MS). The recovery of levoglucosan using this procedure was 69 ± 6% from five filters amended with 2 μg levoglu-cosan, and the reproducibility of the assay is 9%. The limit of detection is ～0.1 μg/mL, which is equivalent to ～3.5 ng/m³ for a 10 L/min sampler or ～8.7 ng/m³ for a 4 L/min personal sampler (assuming 24-hr integrated samples). We demonstrated that levoglucosan concentrations in collocated samples (expressed as ng/m³) were identical irrespective of whether samples were collected by PM with aerodynamic diameter ≤2.5 μm or PM with aerodynamic diameter ≤10 μm impactors. It was also demonstrated that X-ray fluorescence analysis of samples of atmospheric PM, before levoglucosan determinations, did not alter the levels of levoglucosan.     

Monitoring Deposition of Nitrogen-Containing Compounds in a High-Elevation Forest Canopy

Measurements of airborne (gaseous and aerosol), cloud water, and precipitation concentrations of nitrogen compounds were made at Mt. Mitchell State Park (Mt. Gibbs, ~2006 m MSL), North Carolina, during May through September of 1988 and 1989, An annular denuder system was used to ascertain gaseous (nitric acid, nitrous acid, and ammonia) and particulate (nitrate and ammonium) nitrogen species, and a chemiluminescence nitrogen oxides analyzer was used to measure nitric oxide and nitrogen dioxide. Measurements of NO₃ ^? and NH₄ ⁺ ions in cloud and rain water samples were made during the same time period. Mean concentrations of gaseous nitric acid, nitrous acid, and ammonia were 1.14 μg/m³, 0.3 μg/m³, and 0.62 μg/m³ for 1988, and 1.40 μg/m³,0.3 μg/m³, and 1.47 μg/m³ for 1989, respectively. Fine particulate nitrate and ammonium ranged from 0.02 to 0.21 μg/m³ and 0.01 to 4.72 μg/m³ for 1988, and 0.1 to 0.78 μg/m³ and 0.24 to 2.32 μg/m³ for 1989, respectively. The fine aerosol fraction was dominated by ammonium sulfate particles. Mean concentrations of nitrate and ammonium ions in cloud water samples were 238 and 214 μmol/l in 1988, and 135 and 147 μmol/l in 1989, respectively. Similarly, the concentrations of NO₃ and NH₄ ⁺ in precipitation were 26.4 and 14.0 μmol/l in 1988, and 16.6 and 15.2 μmol/l in 1989, respectively. The mean total nitrogen deposition due to wet, dry, and cloud deposition processes was estimated as ~30 and ~40 kg N/ha/year (i.e., ~10 and ~13 kg N/ha/growing season) for 1988 and 1989. Based on an analytical analysis, deposition to the forest canopy due to cloud interception, precipitation, and dry deposition processes was found to contribute ~60, ~20, and ~20 percent, respectively, of the total nitrogen deposition.     

Response of Tomato Fruiting to Hydrogen Fluoride as Influenced by Calcium Nutrition

Two varieties of tomatoes grown at 40 to 200 ppm calcium were continuously fumigated with HF throughout flowering and fruit development. Fruit size was directly related to the level of calcium nutrition, and within each calcium treatment the fruits on plants subjected to HF at about 6 μg F/m³ were smaller than those on unfumigated plants. The smaller fruit size was associated with partial or complete seedlessness, suggesting that calcium plays an essential role in fertilization with which fluoride may interfere. Fluoride injury to the tomato foliage was most severe at the lowest calcium level. Treatment with HF at about 8 μg F/m³ produced some injury to tomato foliage but had no apparent effect on fruiting. Evidently fluoride can affect plant fruiting, but considering the severity of the HF treatments required, effects on tomato fruiting probably are of little practical significance. The relationship between fluoride injury and calcium nutrition suggests interference with calcium metabolism as a mechanism of fluoride injury to plants.     

Concentration and movement of diazinon in air

Abstract

Airborne concentrations of diazinon were measured in rooms for 21 days after crack and crevice application. Residue levels were largest in treated rooms (38 μg/m³ ) after application, followed by adjacent (1 μg/m³ ) and upper and lower rooms (ca. 0.4 μg/m ). Low levels of diazinon were detected in all rooms 21 days after application. Small amounts of diazinon (corrected to an 8 min application period) were detected on respirator pads ( 2.6 μg) and waist pads (2.3 μg) worn by the applicator.     

Performance evaluation of a tailor-made passive sampler for monitoring of tropospheric ozone

Introduction

This study presents the performance evaluation of a tailor-made passive sampler developed for the monitoring of tropospheric ozone.

Methods

The performance of the passive sampler was tested in the field conditions in terms of accuracy, precision, blank values, detection limit, effects of some parameters such as sampling site characteristics and sampling period on the field blanks, self-consistency, experimental and theoretical uptake rates, shelf life and comparison with commercial passive samplers.

Results

There was an agreement (R ²?=?0.84) between the responses of passive sampler and the continuous automatic analyser. The accuracy of the sampler, expressed as percent relative error, was obtained lower than 15%. Method precision in terms of coefficient of variance for three simultaneously applied passive samplers was 12%. Sampler detection limit was 2.42???g?m^?3 for an exposure period of 1?week, and the sampler can be stored safely for a period of up to 8?weeks before exposure. Satisfactory self-consistency results showed that extended periods gave the same integrated response as a series of short-term samplers run side by side. The uptake rate of ozone was found to be 10.21?mL?min^?1 in a very good agreement with the theoretical uptake rate (10.32?mL?min^?1). The results of the comparison study conducted against a commercially available diffusion tube (Gradko diffusion tube) showed a good linear relationship (R ²?=?0.93) between two passive samplers.

Conclusions

The sampler seems suitable to be used in large-scale measurements of ozone where no data are available or the number of existing automated monitors is not sufficient.     

Field performance evaluation during fog-dominated wintertime of a newly developed denuder-equipped PM1 sampler

This study presents the performance evaluation of a novel denuder-equipped PM₁ (particles having aerodynamic diameter less than 1 μm) sampler, tested during fog-dominated wintertime, in the city of Kanpur, India. One PM₁ sampler and one denuder-equipped PM₁ sampler were co-located to collect ambient PM₁ for 25 days. The mean PM₁ mass concentration measured on foggy days with the PM₁ sampler and the denuder-equipped PM₁ sampler was found to be 165.95 and 135.48 μg/m³, respectively. The mean PM₁ mass concentration measured on clear days with the PM₁ sampler and the denuder-equipped PM₁ sampler was observed to be 159.66 and 125.14 μg/m³, respectively. The mass concentration with denuder-fitted PM₁ sampler for both foggy and clear days was always found less than the PM₁ sampler. The same drift was observed in the concentrations of water-soluble ions and water-soluble organic carbon (WSOC). Moreover, it was observed that the use of denuder leads to a significant reduction in the PM positive artifact. The difference in the concentration of chemical species obtained by two samplers indicates that the PM₁ sampler without denuder had overestimated the concentrations of chemical species in a worst-case scenario by almost 40 %. Denuder-fitted PM₁ sampler can serve as a useful sampling tool in estimating the true values for nitrate, ammonium, potassium, sodium and WSOC present in the ambient PM.     

Residues of 2,4‐D in air samples from Saskatchewan: 1966–1975

Abstract

Residues of 2,4‐D (2,4‐dichlorophenoxyacetic acid) in air samples from several sampling sites in central and southern Saskatchewan during the spraying seasons in the 1966–68 and 1970–75 periods were determined by gas‐liquid Chromatographic techniques. Initially, individual esters of 2,4‐D were characterized by retention times and confirmed further by co‐injection and dual column procedures. Since 1973, however, only total 2,4‐D acid levels in air samples have been determined after esterification to the methyl ester and confirmed by gc/ms techniques whenever possible.

Up to 50% of the daily samples collected during the spraying season at any of the locations and during any given year contained 2,4‐D, with butyl esters being found most frequently. The daily 24‐hr mean atmospheric concentrations of 2,4‐D ranged from 0.01 to 1.22 μg/m³, 0.01 to 13.50 μg/m³, and 0.05 to 0.59 μg/m for the iso‐propyl, mixed butyl and iso‐octyl esters, respectively. Even when the samples were analysed for the total 2,4‐D content, i.e. from 1973 onwards, the maximum level of the total acid reached only 23.14 μg/m. In any given year and at any of the sampling sites, about 30% of the samples contained less than 0.01 μg/m³ of 2,4‐D. In another 40% of the samples, the levels of 2,4‐D ranged from 0.01 to 0.099 yg/m. Only about 30% of the samples contained 2,4‐D concentrations higher than 0.1 μg/m³, with only 10% or less exceeding 1 μg/m³.

None of the samples, obtained with the high volume particu‐late sampler, showed any detectable levels of 2,4‐D, indicating little or no transport of 2,4‐D adsorbed on dust particles or as crystals of amine salts.     

Some Effects of Atmospheric Fluoride on Plant Metabolism

Leaves of Tendergreen bean plants exposed to atmospheric fluoride concentrations in the range 1.7 to 7.6 μg/m³ showed increased levels of enolase and catalase activity and decreased levels of pyruvate and α-ketoglutarate. Phosphoenolpyruvate carboxylase activity and oxalacetate were not affected. The leaves of Milo maize plants exposed to 5.0 μg F/m³ showed increased levels of enolase and pyruvate kinase activity and a decreased level of pyruvate. Oxalacetate and α-ketoglutarate levels were not affected. Catalase activity was increased, then decreased by IIF fumigation. The changes induced by HF were greatest six to 10 days after the start of fumigation and disappeared or decreased in magnitude during the post-fumigation period.     

Measurement and Analysis of the Relationship between Ammonia,Acid Gases,and Fine Particles in Eastern North Carolina

Abstract

An annular denuder system, which consisted of a cyclone separator; two diffusion denuders coated with sodium carbonate and citric acid, respectively; and a filter pack consisting of Teflon and nylon filters in series, was used to measure acid gases, ammonia (NH₃), and fine particles in the atmosphere from April 1998 to March 1999 in eastern North Carolina (i.e., an NH₃?rich environment). The sodium carbonate denuders yielded average acid gas concentrations of 0.23 μg/m³ hydrochloric acid (standard deviation [SD] ± 0.2 μg/m³); 1.14 μg/m³ nitric acid (SD ± 0.81 μg/m³), and 1.61 μg/m³ sulfuric acid (SD ± 1.58 μg/m³). The citric acid denuders yielded an average concentration of 17.89 μg/m³ NH₃ (SD ± 15.03 μg/m³). The filters yielded average fine aerosol concentrations of 1.64 μg/m³ ammonium (NH₄ ⁺;SD ± 1.26 μg/m³); 0.26 μg/m³ chloride (SD ± 0.69 μg/m³), 1.92 μg/m³ nitrate (SD ± 1.09 μg/m³), and 3.18 μg/m³ sulfate (SO₄ ^2?; SD ± 3.12 μg/m³). From seasonal variation, the measured particulates (NH₄ ⁺,SO₄ ^2?, and nitrate) showed larger peak concentrations during summer, suggesting that the gas-to-particle conversion was efficient during summer. The aerosol fraction in this study area indicated the domination of ammonium sulfate particles because of the local abundance of NH₃, and the long-range transport of SO₄ ^2? based on back trajectory analysis. Relative humidity effects on gas-to-particle conversion processes were analyzed by particulate NH₄ ⁺ concentration originally formed from the neutralization processes with the secondary pollutants in the atmosphere.     

Evaluation of Probes Used for Source Sampling of Hydrogen Fluoride

The body of information presented in this paper is directed to those individuals concerned with methods for the sampling and measurement of fluorides contained in stack gases produced during the manufacture of phosphate fertilizer or aluminum. An air stream containing gaseous hydrogen fluoride (HF), at concentrations of from 87 to 1700 µg F m^-3, was generated and passed through 193 to 198 cm lengths of Pyrex glass, type 316 stainless steel, TFE Teflon, and methyl methacrylate-coated aluminum probes at flow rates of 28 I min^-1. HF passing through the probes was collected in deionized water contained in a Greenburg-Smith impinger. The Teflon probe exhibited no loss of HF and no trend toward increased passage of HF with time. Significant amounts of fluoride were lost in 18 out of 20 tests with the methacrylate probe and in 4 out of 20 tests with the Pyrex and stainless steel probes. Trends toward increased passage of HF with time occurred with the latter three probe materials. The selective ion electrode and semiautomated methods gave equivalent results when samples were made alkaline to avoid sorption of fluoride by Tygon tubing used in the semiautomated method. These results demonstrated that a Teflon probe gave the most representative sample of gaseous HF. However, additional tests are needed before a final recommendation is made for a probe to sample fluorides in stack gases.     

Authors’ Reply

ABSTRACT

Exposures of occupants in school buses to on-road vehicle emissions, including emissions from the bus itself, can be substantially greater than those in outdoor settings. A dual tracer method was developed and applied to two school buses in Seattle in 2005 to quantify in-cabin fine particulate matter (PM_2.5) concentrations attributable to the buses' diesel engine tailpipe (DPM_tp) and crankcase vent (PM_ck) emissions. The new method avoids the problem of differentiating bus emissions from chemically identical emissions of other vehicles by using a fuel-based organometallic iridium tracer for engine exhaust and by adding deuterated hexatriacontane to engine oil. Source testing results showed consistent PM:tracer ratios for the primary tracer for each type of emissions. Comparisons of the PM:tracer ratios indicated that there was a small amount of unburned lubricating oil emitted from the tailpipe; however, virtually no diesel fuel combustion products were found in the crankcase emissions. For the limited testing conducted here, although PM_ck emission rates (averages of 0.028 and 0.099 g/km for the two buses) were lower than those from the tailpipe (0.18 and 0.14 g/km), in-cabin PM_ck concentrations averaging 6.8 μg/m³ were higher than DPM_tp (0.91 μg/m³ average). In-cabin DPM_tp and PM_ck concentrations were significantly higher with bus windows closed (1.4 and 12 μg/m³, respectively) as compared with open (0.44 and 1.3 μg/m³, respectively). For comparison, average closed- and open-window in-cabin total PM_2.5 concentrations were 26 and 12 μg/m³, respectively. Despite the relatively short in-cabin sampling times, very high sensitivities were achieved, with detection limits of 0.002 μg/m³ for DPM_tp and 0.05 μg/m³ for PM_ck.

IMPLICATIONS PM_2.5 measurements in two Seattle school buses showed average concentrations of 26 and 12 μg/m³ with windows closed and open, respectively. Virtually all PM_2.5 was car bonaceous. Tracer measurements showed that bus self-pollution contributed approximately 50% of total PM_2.5 concentrations with windows closed and 15% with windows open, with over three-quarters of these contributions attributed to crankcase emissions. Maintaining ventilation in buses clearly reduces total PM_2.5 exposures and that from the buses' own emissions. The dual tracer method now offers researchers a new technique for explicit identification of single source contributions in settings with multiple sources of carbonaceous emissions.     

High-volume Impactor for Sampling Fine and Coarse Particles

Final design, calibration, and field testing have been completed for a new 1.13 m³/min (40 cfm) High-volume Virtual Impactor (HVVI). Field tests have demonstrated that the new classifier/collector works well as an accessory to the existing PM10 Size Selective Inlet high-volume samplers. The HVVI provides two fractions of PM10 mass, both of which are collected by filtration. The fine fraction (0-2.5 μm aero. dia.) Is collected on the standard 20.3 × 25.4 cm (8- × 10-in) high-volume filter; the coarse fraction (2.5-10 μm aero. dia.) is collected on a 5.1 × 15.2 cm (2- × 6-in) filter. Coarse flow through the receiver tubes is limited to 0.057 m³/min (2 cfm), 5 percent of the total flow.

The operating pressure drop across the HVVI stages Is sufficiently high to make changes In pressure across the collection filters Insignificant. The HVVI filter holder assembly facilitates loading/ unloading samples in the laboratory, thus eliminating damage due to handling filters in the field. Size separation characteristics of the HVVI agree well with those for the 16.7 L/min commercially available dichotomous sampler with the 50 percent effectiveness (cut-point) occurring at 2.5 μm. Applying laboratory-determined particle losses to the typical ambient particle mass size distribution described In Federal Register 49, 40 CFR, Part 53, Table D-3, the HVVI fine fraction total mass loss is less than 0.8 percent for liquid particles and less than 0.1 percent for solid particles; coarse fraction total mass loss is less than 2.5 percent for liquid particles, and less than 0.2 percent for solid particles.     

An Automatic Particle Sampler with Beta Gauging

Performance test results and operating characteristics of the Wedding & Associates' (W&A) PM10 Beta Gauge Automated Particle Sampler (Sampler), a U.S. EPA Designated Equivalent Method (Designation No. EQPM-0391-081), are reported. The custom, computer-controlled Sampler utilizes BETASOFT?, a multitasking operating system running the high level language application program. The Sampler employs the Wedding PM10 Inlet (Inlet) and Critical Flow Device (CFD). Analysis, calculations and mechanical control are achieved by use of analog sensing and digital logic. The development and testing program included wind tunnel and field tests to verify experimentally its conformity with theoretical calculations of the relationship of collected mass to 3- particle penetration. Use of a ¹⁴C source and a fast-response detector leads to high sensitivity and precision. The instrument has been tested against the Wedding Reference Method Sampler (Reference Method). The 24-hour means of mass concentration values determined by the Sampler, regressed against 24-hour samples collected with the Reference Method, yielded slopes within 1.2 percent of unity, with intercepts less than 1.5 μg/m³ and coefficients of determination (R²) of 0.99 or higher. Resolution is less than 3 μg/m³.     

Fine particulate (PM2.5) composition in Atlanta, USA: assessment of the particle concentrator-Brigham Young University organic sampling system, PC-BOSS, during the EPA supersite study

Aerosol concentrations of carbonaceous material, sulfate, and nitrate for samples obtained using a newly designed PC-BOSS are reported. The results indicated that PM_2.5 composition in Atlanta was dominated by sulfate and organic material, with low concentrations of particulate nitrate. Observed average particulate component concentrations for the 26-day study period were: sulfate, 12.2 μg/m³ (17.0 μg/m³ as ammonium sulfate); non-volatile organic material, 11.4 μg OM/m³ (assumes organic material, OM, is 61% C); semi-volatile organic compounds (SVOC) lost from particles during sampling, 5.3 μg OM/m³; filter retained nitrate, 0.1 μg/m³ (0.2 μg/m³ as ammonium nitrate); nitrate lost from particles, 0.3 μg/m³ (0.4 μg/m³ as ammonium nitrate); and soot (elemental carbon), 1.5 μg/m³. The PC-BOSS particle concentrator efficiency was obtained by comparison of the PC-BOSS sulfate data with sulfate data obtained from the Federal Reference Method (FRM) sampler. A modification of the PC-BOSS design to allow independent determination of this parameter is recommended.     

Multiple-year black carbon measurements and source apportionment using Delta-C in Rochester,New York

Black carbon (BC), an important component of the atmospheric aerosol, has climatic, environmental, and human health significance. In this study, BC was continuously measured using a two-wavelength aethalometer (370 nm and 880 nm) in Rochester, New York, from January 2007 to December 2010. The monitoring site is adjacent to two major urban highways (I-490 and I-590), where 14% to 21% of the total traffic was heavy-duty diesel vehicles. The annual average BC concentrations were 0.76 μg/m³, 0.67 μg/m³, 0.60 μg/m³, and 0.52 μg/m³ in 2007, 2008, 2009, and 2010, respectively. Positive matrix factorization (PMF) modeling was performed using PM_2.5 elements, sulfate, nitrate, ammonia, elemental carbon (EC), and organic carbon (OC) data from the U.S. Environmental Protection Agency (EPA) speciation network and Delta-C (UVBC_370nm – BC_880nm) data. Delta-C has been previously shown to be a tracer of wood combustion factor. It was used as an input variable in source apportionment models for the first time in this study and was found to play an important role in separating traffic (especially diesel) emissions from wood combustion emissions. The result showed the annual average PM_2.5 concentrations apportioned to diesel emissions in 2007, 2008, 2009, and 2010 were 1.34 μg/m³, 1.25 μg/m³, 1.13 μg/m³, and 0.97 μg/m³, respectively. The BC conditional probability function (CPF) plots show a large contribution from the highway diesel traffic to elevated BC concentrations. The measurements and modeling results suggest an impact of the U.S Environmental Protection Agency (EPA) 2007 Heavy-Duty Highway Rule on the decrease of BC and PM_2.5 concentrations during the study period.

Implications: This study suggests that there was an observable impact of the U.S EPA 2007 Heavy-Duty Highway Rule on the ambient black carbon concentrations in Rochester, New York. Aethalometer Delta-C was used as an input variable in source apportionment models and it allowed the separation of traffic (especially diesel) emissions from wood combustion emissions.     

Characterization of air manganese exposure estimates for residents in two Ohio towns

This study was conducted to derive receptor-specific outdoor exposure concentrations of total suspended particulate (TSP) and respirable (d_ae ≤ 10 µm) air manganese (air-Mn) for East Liverpool and Marietta (Ohio) in the absence of facility emissions data, but where long-term air measurements were available. Our “site-surface area emissions method” used U.S. Environmental Protection Agency’s (EPA) AERMOD (AMS/EPA Regulatory Model) dispersion model and air measurement data to estimate concentrations for residential receptor sites in the two communities. Modeled concentrations were used to create ratios between receptor points and calibrated using measured data from local air monitoring stations. Estimated outdoor air-Mn concentrations were derived for individual study subjects in both towns. The mean estimated long-term air-Mn exposure levels for total suspended particulate were 0.35 μg/m³ (geometric mean [GM]) and 0.88 μg/m³ (arithmetic mean [AM]) in East Liverpool (range: 0.014–6.32 μg/m³) and 0.17 μg/m³ (GM) and 0.21 μg/m³ (AM) in Marietta (range: 0.03–1.61 μg/m³). Modeled results compared well with averaged ambient air measurements from local air monitoring stations. Exposure to respirable Mn particulate matter (PM₁₀; PM <10 μm) was higher in Marietta residents.

Implications: Few available studies evaluate long-term health outcomes from inhalational manganese (Mn) exposure in residential populations, due in part to challenges in measuring individual exposures. Local long-term air measurements provide the means to calibrate models used in estimating long-term exposures. Furthermore, this combination of modeling and ambient air sampling can be used to derive receptor-specific exposure estimates even in the absence of source emissions data for use in human health outcome studies.     

Characterization of the Sunset Semi-Continuous Carbon Aerosol Analyzer

Abstract

The field-deployable Sunset Semi-Continuous Organic Carbon/Elemental Carbon (Sunset OCEC) aerosol analyzer utilizes the modified National Institute for Occupational Safety and Health thermal-optical method to determine total carbon (TC), organic carbon (OC), and elemental carbon (EC) at near real-time. Two sets of OC and EC are available: thermal OC and EC, and optical OC and EC. The former is obtained by the thermal-optical approach, and the latter is obtained by directly determining EC optically and deriving optical OC from TC. However, the performance of the Sunset OCEC is not yet fully characterized. Two collocated Sunset OCEC analyzers, Unit A and Unit B, were used to determine the pooled relative standard deviation (RSD) and limit of detection (LOD) between September 18 and November 6, 2007 in Richland, WA. The LOD of Unit A was approximately 0.2 μgC/m³ (0.1 μgC/cm²) for TC, optical OC, and thermal OC, and 0.01 μgC/m³ (0.01 μgC/cm²) for optical EC. Similarly, Unit B had an LOD of approximately 0.3 μgC/m³ (0.2 μgC/cm²) for TC, optical OC, and thermal OC, and 0.02 μgC/m³ (0.01 μgC/cm²) for optical EC. The LOD for thermal EC is estimated to be 0.2 μgC/m³ (0.1 μgC/cm²) for both units. The pooled RSDs were 4.9% for TC (carbon mass loadings 0.6–6.0 μgC/cm²), 5.6% for optical OC (carbon mass loadings 0.6–5.4 μgC/cm²), 5.3% for thermal OC (carbon mass loadings 0.6–5.3 μgC/cm²), and 9.6% for optical EC (carbon mass loadings 0–1.4 μgC/cm²), which indicates good precision between the instruments. The RSD for thermal EC is higher at 24.3% (carbon mass loadings 0–1.2 μgC/cm²). Low EC mass loadings in Richland contributed to the poor RSD of EC. The authors found that excessive noise from the nondispersive infrared (NDIR) laser in the Sunset OCEC analyzer could result in a worsened determination of OC and EC. It is recommended that a “quieter” NDIR laser and detector be used in the Sunset OCEC analyzer to improve quantification. Future work should re-evaluate the precision of the EC parameters in an environment favorable for EC collection. Investigation among quantification differences using various thermal-optical protocols to determine OC and EC is also in need.     

A new sampler for collecting separate dry and wet atmospheric depositions of trace organic chemicals

Studies conducted in Saskatchewan and elsewhere have demonstrated the atmospheric transport of agricultural pesticides and other organic contaminants and their deposition into aquatic ecosystems. To date these studies have focused on ambient concentrations in the atmosphere and in wet precipitation. To measure the dry deposition of organic chemicals, a new sampler was designed which uses a moving sheet of water to passively trap dry particles and gasses. The moving sheet of water drains into a reservoir and, during recirculation through the sampler, is passed through an XAD-2 resin column which adsorbs the trapped organic contaminants. All surfaces which contact the process water are stainless steel or Teflon. Chemicals collected can be related to airborne materials depositing into aquatic ecosystems. The sampler has received a United States patent (number 5,413,003 – 9 May 1996) with the Canadian patent pending.XAD-2 resin adsorption efficiencies for 10 or 50 μg fortifications of ten pesticides ranged from 76% for atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) to 110% for triallate [S-(2,3,3-trichloro-2-phenyl)bis(1-methylethyl)carbamothioate], dicamba (2-methoxy-3,6-dichlorobenzoic acid) and toxaphene (chlorinated camphene mixture). Field testing using duplicate samplers showed good reproducibility and amounts trapped were consistent with those from high volume and bulk pan samplers located on the same site. Average atmospheric dry deposition rates of three chemicals, collected for 5 weeks in May and June, were: dicamba, 69 ng m^-2 da^-1; 2,4-D (2,4-dichlorophenoxyacetic acid), 276 ng m^-2 da^-1: and, γ-HCH (γ-1, 2, 3, 4, 5, 6-hexachlorocyclohexane), 327 ng m^-2 da^-1.     

Graduate Education for Air Pollution Control Personnel

Tendergreen bean plants were grown from seeding to seed maturity under continuous exposure to HF gas at fairly uniform concentrations averaging 0.58, 2.1, 9.1, and 10.5 µg F/m³. Progeny of these plants and of comparable control plants were grown in a clean atmosphere to determine if subsequent generations were affected by HF treatment of the parents.

No effects of HF were found among the progeny of the plants grown at 0.58 µg F/m³. The F₁ generation progeny of the other HF treated plants were less vigorous than control plant progeny, as shown by later emergence, smaller primary leaves, and slower stem growth. This probably was a consequence of the lower starch content of the seed of the HF treated plants. The primary leaves of some F₁ progeny of the plants grown in the three highest HF treatments were severely stunted and distorted. This also may have been due to the low starch content of the seed, or perhaps it resulted from damage to the plumules in shriveled, distorted seed produced in these treatments.

Some of the early trifoliate leaves of many F₁ generation progeny of the plants grown at 2.1 µg F/m³ and higher were abnormal in the separation and number of their leaflets. This abnormality apparently was heritable, for in the next (F₂) generation it occurred most frequently among plants whose parents were abnormal. However, considerably fewer F₃ generation plants had abnormal trifoliate leaves, indicating rapid reversal to the normal form.