Evaluation of a personal air sampler for twenty-four hour collection of fine particles and semivolatile organics.

The U.S. EPA has conducted an evaluation of a commercially available lightweight fine particle personal sampler for use in human exposure and biomarker studies involving 24-h collections of particulate matter, particle-bound organics such as polycyclic aromatic hydrocarbons (PAHs), and semivolatile organics (PAHs). Independent laboratory evaluation of the prototype design, intended to produce a 2.5-micron aerodynamic diameter cut-point at a flow between 1.5 and 1.7 lpm (liters per minute), indicated that at a challenge flow rate of 1.5 lpm, the sampler provided an aerodynamic cut-point (dp50) of only 1.7 microns. The variance between expected size selection resulted from the prototype's jet diameter dimension being inadvertently based upon a flow rate of 2.0 lpm rather than an intended 1.5-1.7 lpm. Other aerodynamic factors not presently accounted for may also have played an influence. Extrapolated cut-points for flow rates at 1 and 3 lpm for the prototype were determined to be 2.1 and 1.2 microns, respectively. Total losses attributed to unwanted particle retention within the sampler ranged from 10% for 0.91 micron size particles to essentially zero approaching diameters greater than 2.0 microns. The ambient concentration of particles (< 1.7 microns) needed for acceptable gravimetric filter measurements involving 24-h sample collection was determined to be 10 micrograms/m3. Investigation of the sampler to retain and recover PAHs using XAD-2 resin, often of importance in human exposure biomarker studies, indicated that corrected recoveries between 94% and 108% could be obtained for 16 priority pollutant PAH species. Overall evaluation of the personal monitor indicates that it has research utility due to its modular features and size but reconfiguration should be performed that would permit true PM2.5 size selection. The current configuration collects particles less than 2.5 microns at approximately 95% collection efficiency.

Airborne exposures to PAH and PM2.5 particles for road paving workers applying conventional asphalt and crumb rubber modified asphalt.

Personal exposure monitoring was conducted for road paving workers in three states. A research objective was to characterize and compare occupational exposures to fine respirable particles (< 2.5 microns) and particle-bound polycyclic aromatic hydrocarbons (PAHs) for road paving workers applying conventional (petroleum derived) asphalt and asphalt containing crumb rubber from shredded tires. Workers not exposed to asphalt fume were also included for comparison (to support the biomarker component of this study). The rubber content of the crumb rubber modified (CRM) asphalt at the three study sites was 12, 15, and 20%. A comparison of some specific job categories from two sites indicates greater potential carcinogenic PAH exposures during CRM asphalt work, however, the site with the greatest overall exposures did not indicate any differences for specific jobs. A statistical analysis of means for fine particle, pyrene and total carcinogenic PAH personal exposure shows, with two exceptions, there were no differences in exposures for these three measurement variables. One site shows significantly elevated pyrene exposure for CRM asphalt workers and another site similarly shows greater carcinogenic PAH exposure for CRM asphalt workers. Conventional and CRM asphalt worker airborne exposures to the PAH carcinogen marker, BaP, were very low with concentrations comparable to ambient air in many cities. However, this study demonstrates that asphalt road paving workers are exposed to elevated airborne concentrations of a group of unknown compounds that likely consist of the carcinogenic PAHs benz(a)anthracene, chrysene and methylated derivatives of both. The research described in this article has been reviewed in accordance with U.S. Environmental Protection Agency policy and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use.

Development of source testing, analytical, and mutagenicity bioassay procedures for evaluating emissions from municipal and hospital waste combustors.

Incineration is currently being used for disposal of about 10% of the solid waste generated in the United States, and this percentage will likely increase as land disposal declines. Siting new incinerators, however, is often controversial because of concerns related to the possibility of adverse health effects and environmental contamination from long-term exposure to stack emissions. Specific concerns relate to the adequacies of a) stack emission testing protocols, b) existing regulations, and c) compliance monitoring and enforcement of regulations. U.S. Environmental Protection Agency laboratories are cooperatively conducting research aimed at developing new testing equipment and procedures that will allow a more comprehensive assessment of the complex mixture of organics that is present in stack emissions. These efforts are directed specifically toward developing source testing equipment and procedures, analytical procedures, and bioassay procedures. The objectives of this study were to field test two types of high-volume source dilution samplers, collect stack samples for use in developing analytical and mutagenicity bioassay procedures, and determine mutagenicity of organics associated with emission particles from two municipal waste combustors and a hospital waste combustor. Data are presented for particle concentrations and emission rates, extractable organic concentrations and emission rates, and Salmonella (Ames) mutagenic potency and emission rates. The mutagenic emission rates and emission factors are compared to other incinerators and combustion sources.

Effects of operating variables on PAH emissions and mutagenicity of emissions from woodstoves.

As part of the Integrated Air Cancer Project, the U.S. Environmental Protection Agency (EPA) has conducted field emission measurement programs in Raleigh, North Carolina, and Boise, Idaho, to identify the potential mutagenic impact of residential wood burning and motor vehicles on ambient and indoor air. These studies included the collection of emission samples from chimneys serving wood burning appliances. Parallel projects were undertaken in instrumented woodstove test laboratories to quantify woodstove emissions during operations typical of in-house usage but under more controlled conditions. Three woodstoves were operated in test laboratories over a range of burnrates, burning eastern oak, southern yellow pine, or western white pine. Two conventional stoves were tested at an altitude of 90 m. One of the conventional stoves and a catalytic stove were tested at an altitude of 825 m. Decreasing burnrate increased total particulate emissions from the conventional stoves while the catalytic stove's total particulate emissions were unaffected. There was no correlation of total particulate emissions with altitude whereas total polynuclear aromatic hydrocarbon (PAH) emissions were higher at the lower altitude. Mutagenicity of the catalytic stove emissions was higher than emissions from the conventional stove. Emissions from burning pine were more mutagenic than emissions from oak.

Evaluation of high volume particle sampling and sample handling protocols for ambient urban air mutagenicity determinations.

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM10 Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22 degrees C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at -70 degrees C to -80 degrees C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set.(ABSTRACT TRUNCATED AT 250 WORDS)

Cotinine analytical workshop report: consideration of analytical methods for determining cotinine in human body fluids as a measure of passive exposure to tobacco smoke.

A two-day technical workshop was convened November 10-11, 1986, to discuss analytical approaches for determining trace amounts of cotinine in human body fluids resulting from passive exposure to environmental tobacco smoke (ETS). The workshop, jointly sponsored by the U.S. Environmental Protection Agency and Centers for Disease Control, was attended by scientists with expertise in cotinine analytical methodology and/or conduct of human monitoring studies related to ETS. The workshop format included technical presentations, separate panel discussions on chromatography and immunoassay analytical approaches, and group discussions related to the quality assurance/quality control aspects of future monitoring programs. This report presents a consensus of opinion on general issues before the workshop panel participants and also a detailed comparison of several analytical approaches being used by the various represented laboratories. The salient features of the chromatography and immunoassay analytical methods are discussed separately.

Sample accountability quality assurance for the "Integrated Air Cancer Project" research program of the U.S. Environmental Protection Agency.

A sample accountability quality assurance (QA) program is described for a field and laboratory research effort which resulted in collection of approximately 2000 samples for analysis by several EPA and contractor laboratories. A QA program was specifically developed for this research program to include sample transfer from collection site to storage maintenance, record development, transfer to researchers, and sample tracking at all stages. A sample identification system and sample custody records are described for field and laboratory application. The functions of a sample coordinator are also described as relating to sample custody, coordination of sample analysis with researchers, and development of computer record files to facilitate research and sample tracking.

A method for the determination of dialkyl phosphate residues in urine.

The analysis of urine for dialkyl phosphate residues provides a measure of mammalian exposure to organophosphate pesticides. A method is presented for quantitative determination of six alkyl phosphate urinary metabolites. These metabolites are as follows: O,O-dimethyl phosphate, O,O-diethyl phosphate, O,O-dimethyl phosphorothionate, O,O-dimethyl phosphorodithioate, O,O-diethyl phosphorothionate, and O,O-diethyl phosphorodithioate. A screening method is also given for a rapid assessment of human exposure. Pentafluorobenzyl bromide is utilized as the derivatization reagent to form pentafluorobenzyl esters. The reaction products are determined by gas chromatography on routine pesticide columns utilizing the phosphorus specific flame photometric detector. Recoveries of all six dialkyl phosphates are greater than 90% with the minimum level of detection ranging from 0.04 to 0.13 ppm.

Improved method for hexachlorobenzene and mirex determination with hexachlorobenzene confirmation in adipose tissue: collaborative study.

A previously published method for determination and confirmation of hexachlorobenzene (HCB) in adipose tissue was also applied to mirex residues. A modified procedure for both residues was collaboratively studied by 12 laboratoires. The procedure specifies direct application of an extracted or rendered fat sample to a Florisil cleanup column and one-fraction elution. Mirex and HCB are determined by direct GLC of the concentrated eluate. HCB residues are then confirmed by reaction with isopropanol to form the disubstituted bis-isopropoxytetrachlorobenzene (BITB) derivative. Mirex residues are destroyed by this reaction. All participants were asked to analyze an unknown standard mixture of HCB and mirex and 10 rendered chicken fat samples consisting of one blank and 9 samples fortified samples represented 3 samples at each of 3 fortification levels. The HCB fortifications of 20.0, 33.3, and 50.0 ppb yielded average interlaboratory recoveries of 89.6, 87.4, and 92.6%, respectively. The respective coefficients of variation (CV) for HCB results were 9.1, 6,8, and 10.0%. The mirex fortifications of 150, 300, and 500 ppb yielded average interlaboratory recoveries of 89.0, 90.2, and 92.3%, respectively. The respective CV values for mirex results were 7.6, 16.5, and 18.1%. The method has been adopted official first action.

Gas-liquid chromatography and liquid chromatography of ethylenethiourea in fresh vegetable crops, fruits, milk, and cooked foods.

The Onley-Yip procedure for determining ethylenethiourea (ETU) in milk and crops was modified to reduce interferences by the ethylenebisdithiocarbamates (EBDCs). A 20 g crop-methanol extract is cleaned up by adsorbing the sample onto Gas-Chrom S. desorbing ETU, and eluting ETU from aluminum oxide with chloroform containing ethanol. ETU is converted to the S-butyl derivative for gas-liquid chromatography (GLC) and flame photometric detection (sulfur mode). For liquid chromatography (LC), ETU is cleaned up on another aluminum oxide column and injected directly. LC and GLC results are confirmed by thin layer chromatography. A cooking procedure based on conversion of EBDCs to ETU is included for surveying crops for possible EBDC content. Recoveries from 8 crops and milk fortified at 0.05 ppm ETU ranged from 73 to 100%.

Residues in broiler chick tissues from low level feedings of seven chlorinated hydrocarbon insecticides.

Two chlorinated insecticide feeding studies from 1967-1968, using broiler chicks, have been completed. In Study I, lindane, heptachlor epoxide, dieldrin, endrin, methoxychlor, and DDT were fed in combination at 3 levels: 0.05, 0.15, and 0.45 ppm. Data show that, in fat tissues, heptachlor epoxide attained a level approximately 20 times the respective levels in the feed; dieldrin 15 times; endrin 10 times; p,p'-DDT 9 times; lindane 3 times; and o.p'-DDT less than the feeding levels. Of the DDT metabolites, p.p'-DDE and p,p'-DDD, only p,p'-DDE was significant at 3 times the 0.45 ppm feeding level. Endrin ketone, a metabolite of endrin, reached plateau levels approximately equal to feeding levels. All residue levels in liver tissues were less than 0.02 ppm. In Study II, technical chlordane was fed singly at the 0.05, 0.15, and 0.45 ppm levels. Results are tabulated for both total chlordane and for 6 identifiable isomers. Total chlordane in fat tissues attained plateau levels 3-5 times the respective feeding levels. Total chlordane levels in liver and breast tissues were all less than 0.01 ppm.