Arizona Hazardous Air Pollutants Monitoring Program

ABSTRACT

In order to evaluate the existing risk to public health in Arizona related to hazardous air pollution, ambient air monitoring for selected hazardous air pollutants (HAPs) was carried out in 1994-1996 in several representative urban and rural areas of Arizona. A wide range of organic HAPs was monitored, requiring a variety of sampling and analysis methods. Stainless steel SUMMA canisters were used for collection of volatile hydrocarbons and halocarbons, which were analyzed by capillary gas chromatography with flame ionization and electron capture detection (GC-FID/ECD). Carbonyl compounds were collected using 2,4-dinitrophenylhydrazine-impregnated cartridges and analyzed by high performance liquid chromatog-raphy with ultraviolet detection. Semi-volatile and non-volatile polycyclic aromatic compounds were collected using a sampling train consisting of a filter followed by a PUF/XAD-4/PUF sandwich cartridge. Following extraction, samples were analyzed by capillary GC with mass spectrometric detection (GC-MS). Database software was developed for data processing and reporting functions. This paper describes the sampling strategy and the sampling and analysis methods employed in the monitoring program and presents a summary of all the results obtained during the duration of the sampling program.     

Evaluation of sample recovery of malodorous livestock gases from air sampling bags, solid-phase microextraction fibers, Tenax TA sorbent tubes, and sampling canisters

Odorous gases associated with livestock operations are complex mixtures of hundreds if not thousands of compounds. Research is needed to know how best to sample and analyze these compounds. The main objective of this research was to compare recoveries of a standard gas mixture of 11 odorous compounds from the Carboxen/PDMS 75-microm solid-phase microextraction fibers, polyvinyl fluoride (PVF; Tedlar), fluorinated ethylene propylene copolymer (FEP; Teflon), foil, and polyethylene terephthalate (PET; Melinex) air sampling bags, sorbent 2,b-diphenylene-oxide polymer resin (Tenax TA) tubes, and standard 6-L Stabilizer sampling canisters after sample storage for 0.5, 24, and 120 (for sorbent tubes only) hrs at room temperature. The standard gas mixture consisted of 7 volatile fatty acids (VFAs) from acetic to hexanoic, and 4 semivolatile organic compounds including p-cresol, indole, 4-ethylphenol, and 2'-aminoacetophenone with concentrations ranging from 5.1 ppb for indole to 1270 ppb for acetic acid. On average, SPME had the highest mean recovery for all 11 gases of 106.2%, and 98.3% for 0.5- and 24-hr sample storage time, respectively. This was followed by the Tenax TA sorbent tubes (94.8% and 88.3%) for 24 and 120 hr, respectively; PET bags (71.7% and 47.2%), FEP bags (75.4% and 39.4%), commercial Tedlar bags (67.6% and 22.7%), in-house-made Tedlar bags (47.3% and 37.4%), foil bags (16.4% and 4.3%), and canisters (4.2% and 0.5%), for 0.5 and 24 hr, respectively. VFAs had higher recoveries than semivolatile organic compounds for all of the bags and canisters. New FEP bags and new foil bags had the lowest and the highest amounts of chemical impurities, respectively. New commercial Tedlar bags had measurable concentrations of N,N-dimethyl acetamide and phenol. Foil bags had measurable concentrations of acetic, propionic, butyric, valeric, and hexanoic acids.     

Evaluation of adsorbent sampling tube materials and Tenax-TA for analysis of volatile biogenic organic compounds

Adsorbent tube materials, bed retainers and Tenax-TA were evaluated for their respective roles in adsorbing biogenic volatile organic compounds from air and their tendencies to cause chemical transformation of analytes upon thermal desorption. Stainless steel, Silcosteel^® and Sulfinert^® treated stainless steel tubes exhibited varying degrees of adsorption and reactivity towards some analytes. However, the typical short exposure of the sample stream to wall material before entering an adsorbent bed, minimizes the effect of these properties. Three forms of silica wool (untreated glass wool and siloxane-treated glass and fused silica wool), often used as adsorbent bed retainers, were evaluated and found to function as an adsorbent bed especially for oxygenated monoterpenes and sesquiterpenes. Tenax-TA was evaluated in stainless steel tubes (untreated and treated) with a 2 μm mesh woven wire disk (also untreated and treated) to circumvent the effects of using a silica wool bed retainer. Tenax-TA adsorbent in stainless steel, Silcosteel and Sulfinert tubes yielded equivalent results when compared with direct (cryogenic) pre-concentration analysis of a multi-component mixture of n-alkanes and selected biogenic VOC. Tenax-TA tubes that had been used for 15–20 bake out–sample–desorption cycles (field and laboratory sampling) were compared with freshly packed tubes and found to give equivalent results.     

Characteristics of Oil Field Emissions in the Vicinity of Tulsa,Oklahoma

In 1988 a study was undertaken in the vicinity of Tulsa, Oklahoma to determine the characteristics, composition, and relative concentrations of the oil field emissions of volatile organic compounds (VOC). Forty grab samples (10-minute) using stainless steel canisters were collected from five different stages of crude oil production over an 80-day period (August-October). The samples were analyzed at the Tulsa City-County Health Department’s laboratory, using cryogenic preconcentration, gas chromatographic separation, and flame ionization detection. The six prevalent components of the oil field emissions were ethane, propane, 2- methyl propane, n-butane, 2-methylbutane, and n-pentane with propane predominating. The composition is unique with higher amounts of propane than ethane and is different from natural gas which has more abundant ethane. Decreases occurred in the amounts of light compounds, namely, ethane and propane from well heads through refinery tanks. The bulk of these losses appeared to be at the well heads and gathering tanks.     

Evaluation of Sample Recovery of Malodorous Livestock Gases from Air Sampling Bags,Solid-Phase Microextraction Fibers,Tenax TA Sorbent Tubes,and Sampling Canisters

Abstract

Odorous gases associated with livestock operations are complex mixtures of hundreds if not thousands of compounds. Research is needed to know how best to sample and analyze these compounds. The main objective of this research was to compare recoveries of a standard gas mixture of 11 odorous compounds from the Carboxen/PDMS 75–μm solid–phase microextraction fibers, polyvinyl fluo–ride (PVF; Tedlar), fluorinated ethylene propylene copolymer (FEP; Teflon), foil, and polyethylene terephthalate (PET; Melinex) air sampling bags, sorbent 2,b–diphenylene–oxide polymer resin (Tenax TA) tubes, and standard 6–L Stabilizer sampling canisters after sample storage for 0.5, 24, and 120 (for sorbent tubes only) hrs at room temperature. The standard gas mixture consisted of 7 volatile fatty acids (VFAs) from acetic to hexanoic, and 4 semivolatile organic compounds including p–cresol, indole, 4–ethylphenol, and 2'–aminoacetophenone with concentrations ranging from 5.1 ppb for indole to 1270 ppb for acetic acid. On average, SPME had the highest mean recovery for all 11 gases of 106.2%, and 98.3% for 0.5– and 24–hr sample storage time, respectively. This was followed by the Tenax TA sorbent tubes (94.8% and 88.3%) for 24 and 120 hr, respectively; PET bags (71.7% and 47.2%), FEP bags (75.4% and 39.4%), commercial Tedlar bags (67.6% and 22.7%), in–house–made Tedlar bags (47.3% and 37.4%), foil bags (16.4% and 4.3%), and canisters (4.2% and 0.5%), for 0.5 and 24 hr, respectively. VFAs had higher recoveries than semivolatile organic compounds for all of the bags and canisters. New FEP bags and new foil bags had the lowest and the highest amounts of chemical impurities, respectively. New commercial Tedlar bags had measurable concentrations of N,N–dimethyl acetamide and phenol. Foil bags had measurable concentrations of acetic, propionic, butyric, valeric, and hexanoic acids.     

Evaluation of non-enteric sources of non-methane volatile organic compound (NMVOC) emissions from dairies

Dairies are believed to be a major source of volatile organic compounds (VOC) in Central California, but few studies have characterized VOC emissions from these facilities. In this work, samples were collected from six sources of VOCs (Silage, Total Mixed Rations, Lagoons, Flushing Lanes, Open Lots and Bedding) at six dairies in Central California during 2006–2007 using emission isolation flux chambers and polished stainless steel canisters. Samples were analyzed by gas chromatography/mass spectrometry and gas chromatography/flame ionization detection. Forty-eight VOCs were identified and quantified in the samples, including alcohols, carbonyls, alkanes and aromatics. Silage and Total Mixed Rations are the dominant sources of VOCs tested, with ethanol as the major VOC present. Emissions from the remaining sources are two to three orders of magnitude smaller, with carbonyls and aromatics as the main components. The data suggest that animal feed rather than animal waste are the main source of non-enteric VOC emissions from dairies.     

Application of a purge and trap TDS-GC/MS procedure for the determination of emissions from flame retarded polymers

Emissions of volatile organic compounds (VOCs) from different thermoplastic polymers used in electrotechnical applications were investigated using a purge and trap procedure that involved adsorption on Tenax GR. Results were compared to those for an operating TV set monitored in a test chamber. The analyses were in both cases carried out using thermodesorption gas chromatography with mass spectrometric detection (TDS-GC/MS). Substances identified were monomers, volatile additives, or related compounds. Special attention was given to the detection of halogenated compounds. Their origin was studied using reference samples and synthetic standards.     

Evaluation of an In Situ,On-Line Purging System for the Cone Penetrometer

Abstract

Materials that will be used to construct an in situ, on-line purging system for the cone penetrometer were evaluated. Transfer efficiencies for volatile organic compounds (VOCs) through stainless steel, nickel, aluminum, and Teflon® tubings were determined using a gas-phase mixture of VOCs containing trichloromethane, tetrachloromethane, 1,1,1- trichloroethane, tetrachloroethene, hexane, benzene, toluene, and 1,2-dimethylbenzene. The water content of the gas stream had an insignificant effect on the quantitative transfer of VOCs through Teflon® tubing but was critical to efficiently transfer the compounds through metal tubing, particularly nickel. Transfer efficiencies for all eight analytes in moist gas streams through stainless steel were greater than 95%. Toluene, tetrachloroethene, and 1,2-dimethylbenzene were transferred with 93%, 81%, and 80% efficiency, respectively, when they were drawn through Teflon® PFA (perfluoroalkoxy) tubing. In general, the retention of the VOCs by Teflon® increases with decreasing aqueous solubility of the analyte. The efficiencies at which VOCs were purged from aqueous standards in Teflon® PFA, Type 304 stainless steel, and glass vessels were similar. Stainless steel was superior to nickel, aluminum, and the Teflon® polymers as a material for an in situ, on-line purging system for the cone penetrometer.     

污泥含炭吸附剂对挥发性有机废气吸附实验研究

研究了污泥含炭吸附剂对挥发性有机污染物的吸附特性。结果表明,污泥含炭吸附剂对苯系物的吸附为典型的物理吸附,其吸附甲苯等温线的类型系优惠型吸附等温线,表明具有良好的吸附能力;在吸附反应温度为20℃,气体流量为500 mL/m in(停留时间为0.424 s),甲苯浓度为2 700 mg/m3时,甲苯的饱和吸附容量为150.0 mg/g;同时,研究表明污泥含炭吸附剂对苯系物的饱和吸附容量和吸附强弱次序为二甲苯甲苯苯。结果表明污泥含炭吸附剂适合对中低浓度有机废气的吸附净化。     

Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Ozone artifacts and carbonyl measurements using Tenax GR, Tenax TA, Carbopack B, and Carbopack X adsorbents

Four popular thermally desorbable adsorbents used for air sampling (Tenax TA, Tenax GR, Carbopack B, and Carbopack X) are examined for the potential to form artifacts with ozone (O3) at environmental concentrations. The performance of these adsorbents for the ketone and aldehyde species identified as O3-adsorbent artifacts was also characterized, including recovery, linearity, and method detection limits (MDLs). Using gas chromatography/mass spectrometry, 13 different artifacts were identified and confirmed for both Tenax TA and Tenax GR, 9 for Carbopack B, but none for Carbopack X. Several O3 artifacts not reported previously were identified, including: pentanal, 3-hexanone, 2-hexanone, hexanal, 3-heptanone, and heptanal with Tenax TA; pentanal, 3-hexanone, 2-hexanone, hexanal, and 3-heptanone on Tenax GR; and 1-octene and 1-nonene with Carbopack B. Levels of straight-chain aldehyde artifacts rapidly diminished after a few cycles of adsorbent conditioning/O3 exposure, and concentrations could be predicted using a first-order model. Phenyl-substituted carbonyl artifacts (benzaldehyde and acetophenone) persisted on Tenax TA and GR even after 10 O3 exposure-conditioning cycles. O3 breakthrough through the adsorbent bed was most rapid in adsorbents that yielded the highest levels of artifacts. Overall, artifact composition and concentration are shown to depend on O3 concentration and dose, conditioning method, and adsorbent type and age. Calibrations showed good linearity, and most compounds had reasonable recoveries, for example, 90 +/- 15% for Tenax TA, 97 +/- 23% for Tenax GR, 101 +/- 24% for Carbopack B, and 79 +/- 25% (91 +/- 9% for n-aldehydes) for Carbopack X. Benzeneacetaldehyde recovery was notably poorer (22-63% across the four adsorbents). MDLs for several compounds were relatively high, up to 5 ng. By accounting for both artifact formation and method performance, this work helps to identify which carbonyl compounds can be measured using thermally desorbable adsorbents and which may be prone to bias because of the formation of O3-adsorbent artifacts.     

Ozone Artifacts and Carbonyl Measurements Using Tenax GR,Tenax TA,Carbopack B,and Carbopack X Adsorbents

Abstract

Four popular thermally desorbable adsorbents used for air sampling (Tenax TA, Tenax GR, Carbopack B, and Carbopack X) are examined for the potential to form artifacts with ozone (O₃) at environmental concentrations. The performance of these adsorbents for the ketone and alde-hyde species identified as O₃-adsorbent artifacts was also characterized, including recovery, linearity, and method detection limits (MDLs). Using gas chromatography/mass spectrometry, 13 different artifacts were identified and confirmed for both Tenax TA and Tenax GR, 9 for Carbopack B, but none for Carbopack X. Several O₃ artifacts not reported previously were identified, including: pentanal, 3-hexanone, 2-hexanone, hexanal, 3-heptanone, and heptanal with Tenax TA; pentanal, 3-hexanone, 2-hexanone, hexanal, and 3-heptanone on Tenax GR; and 1-octene and 1-nonene with Carbopack B. Levels of straight-chain aldehyde artifacts rapidly diminished after a few cycles of adsorbent conditioning/O₃ exposure, and concentrations could be predicted using a first-order model. Phenyl-substituted carbonyl artifacts (benzalde-hyde and acetophenone) persisted on Tenax TA and GR even after 10 O₃ exposure-conditioning cycles. O₃ breakthrough through the adsorbent bed was most rapid in adsorbents that yielded the highest levels of artifacts. Overall, artifact composition and concentration are shown to depend on O₃ concentration and dose, conditioning method, and adsorbent type and age. Calibrations showed good linearity, and most compounds had reasonable recoveries, for example, 90 ±15% for Tenax TA, 97 ±23% for Tenax GR, 101 ±24% for Carbopack B, and 79 ±25% (91 ±9% for n-aldehydes) for Carbopack X. Benzeneacetaldehyde recovery was notably poorer (22–63% across the four adsorbents). MDLs for several compounds were relatively high, up to 5 ng. By accounting for both artifact formation and method performance, this work helps to identify which carbonyl compounds can be measured using thermally desorbable adsorbents and which may be prone to bias because of the formation of O_3- adsorbent artifacts.     

Sampling and Analysis of Volatile Organic Compounds Evolved During Thermal Processing of Acrylonitrile Butadiene Styrene Composite Resins

Abstract

The evaluation of emissions of volatile organic compounds (VOCs) during processing of resins is of interest to resin manufacturers and resin processors. An accurate estimate of the VOCs emitted from resin processing has been difficult due to the wide variation in processing facilities. This study was designed to estimate the emissions in terms of mass of emitted VOC per mass of resin processed.

A collection and analysis method was developed and validated for the determination of VOCs present in the emissions of thermally processed acrylonitrile butadiene styrene (ABS) resins. Four composite resins were blended from automotive, general molding, pipe, and refrigeration grade ABS resins obtained from the manufacturers. Emission samples were collected in evacuated 6-L Summa canisters and then analyzed using gas chromatography/flame ionization detection/mass selective detection (GC/FID/MSD). Levels were determined for nine target analytes detected in canister samples, and for total VOCs detected by an inline GC/FID. The emissions evolved from the extrusion of each composite resin were expressed in terms of mass of VOCs per mass of processed resin. Styrene was the principal volatile emission from all the composite resins. VOCs analyzed from the pipe resin sample contained the highest level of styrene at 402 μg/g. An additional collection and detection method was used to determine the presence of aerosols in the emissions. This method involved collecting particulates on glass fiber filters, extracting them with solvents, and analyzing them using gas chromatography/mass spectrometry (GC/MS). No significant levels of any of the target analytes were detected on the filters.     

Long-path FTIR Measurements of Volatile Organic Compounds in an Industrial Setting

A long-path Fourier transform spectrometer was used to make measurements of volatile organic compounds in an industrial complex in New Castle, Delaware as part of the Superfund Innovative Technology Evaluation (SITE) program. These data are compared to data taken with a whole-air canister technique. To provide an effective comparison the canisters were transported along the path for a 32-min period. For each FTIR spectrum, 256 interferograms were co-added over a 4-mln period. Eight individual spectra were then co-added to obtain the comparison data.     

Measurement of Volatile Organics at Part per Billion Concentrations Using a Cold Trap Inlet and High Speed Gas Chromatography

Direct inlet gas chromatography (GC) is becoming one of the most frequently used techniques for measurement of volatile organics in air. Although GC is an effective tool, its usefulness as a field method can be limited by retention times of several minutes or more, and by the limits of detection. In order to address these issues, a high speed GC system featuring a capillary cold trap inlet and variable speed electrometeramplifier was developed and tested.

The gas cooled inlet was used to collect and focus organic vapors from injection volumes of up to 1 ml. Resistance heating of the metal cold trap produced a narrow injection band that allowed simple separations to be completed in 5 to 20 seconds. Use of a variable speed electrometer-amplifier allowed the response time and noise suppression characteristics to be adjusted to the needs of the specific analysis.

Simple mixtures of organics including aromatics, alkanes and chlorinated hydrocarbons were separated in 20 seconds or less. The limits of detection for 13 test compounds ranged from less than 1 part per billion by volume (ppbv) to about 50 ppbv. Data presented here indicate that high speed GC using a cold trap inlet may be a feasible approach for near real-time measurement of volatile organics in ambient air.     

Comparison of analytical techniques for the determination of aldehydes in test chambers

The level of carbonyl compounds in indoor air is crucial due to possible health effects and the high prevalence of their potential sources. Therefore, selecting a convenient and rapid analytical technique for the reliable detection of carbonyl compound concentrations is important. The acetyl acetone (acac) method is a widely used standard procedure for detecting gaseous formaldehyde. For measuring formaldehyde along with other carbonyl compounds, the DNPH-method is commonly applied. The recommended procedure for measuring volatile organic compounds (VOCs) is sampling on Tenax TA, followed by thermal desorption and GC/MS analysis. In this study, different analytical techniques for the quantification of formaldehyde, pentanal, and hexanal are critically compared. It was found that the acac- and DNPH-method are in very good agreement for formaldehyde. In contrast, the DNPH-method significantly underestimates indoor air concentrations of the higher aldehydes in comparison to sampling on Tenax TA, although both methods are strongly correlated. The reported results are part of the EURIMA-WKI study on levels of indoor air pollutants resulting from construction, building materials and interior decoration.     

Validation of an evacuated canister method for measuring part-per-billion levels of chemical warfare agent simulants

The National Institute for Occupational Safety and Health (NIOSH) research on direct-reading instruments (DRIs) needed an instantaneous sampling method to provide independent confirmation of the concentrations of chemical warfare agent (CWA) simulants. It was determined that evacuated canisters would be the method of choice. There is no method specifically validated for volatile organic compounds (VOCs) in the NIOSH Manual of Analytical Methods. The purpose of this study was to validate an evacuated canister method for sampling seven specific VOCs that can be used as a simulant for CWA agents (cyclohexane) or influence the DRI measurement of CWA agents (acetone, chloroform, methylene chloride, methyl ethyl ketone, hexane, and carbon tetrachloride [CCl4]). The method used 6-L evacuated stainless-steel fused silica-lined canisters to sample the atmosphere containing VOCs. The contents of the canisters were then introduced into an autosampler/preconcentrator using a microscale purge and trap (MPT) method. The MPT method trapped and concentrated the VOCs in the air sample and removed most of the carbon dioxide and water vapor. After preconcentration, the samples were analyzed using a gas chromatograph with a mass selective detector. The method was tested, evaluated, and validated using the NIOSH recommended guidelines. The evaluation consisted of determining the optimum concentration range for the method; the sample stability over 30 days; and the accuracy, precision, and bias of the method. This method meets the NIOSH guidelines for six of the seven compounds (excluding acetone) tested in the range of 2.3-50 parts per billion (ppb), making it suitable for sampling of these VOCs at the ppb level.     

Carbon bed fires and the use of carbon canisters for air emissions control on fixed-roof tanks

Fixed-roof tanks are used extensively at manufacturing, waste management, and other facilities to store or process liquids containing volatile organic compounds. Federal and state air standards require the control of organic air emissions from many of these tanks. A common practice used for some fixed-roof tanks that are required to use controls is to vent the tank through an activated carbon canister. When organic vapors are adsorbed on activated carbon, heat is released. Under certain conditions, the temperature of the carbon bed can increase to a level at which the carbon or organic vapors spontaneously ignite, starting a fire in the carbon bed. Bed fires in carbon canisters are not uncommon and can present a significant safety hazard at facilities if proper safety measures are not implemented. This article discusses how carbon adsorber bed fires occur and presents general guidance on safety measures for carbon canisters installed on fixed-roof tanks to reduce the likelihood of a carbon bed fire and to minimize the impact in the event of a fire.     

Trapping efficiency of selected adsorbents for various airborne pesticides.

A study was conducted to compare the efficiency of five adsorbents used by government and private laboratories to collect airborne pesticides. Six pesticides, acephate, chlordane, chlorpyrifos, diazinon, heptachlor, and propoxur, were vaporized in a closed system and collected on each of the adsorbents, Chromosorb 102, ORBO 42, ORBO 44 (chlordane and heptachlor only), polyurethane foam (PUF) or Tenax GC, by drawing 250 L of air through the adsorbent. There were no differences in collection efficiency of the five pesticides on Chromosorb 102, ORBO's 42/44, and PUF. The efficiency with Tenax was somewhat less with several of the pesticides.     

Collection of vapors of selected chlorocarbons and benzene on Tenax GC

Breakthrough and retention volume studies have been done for a series of chlorocarbon compounds on Tenax GC adsorbent with results compared to data of other workers. Initial data indicates that carrier velocity (Time to establish equilibrium) may significantly effect retention of these chemicals.