United States
Environmental Protection
Agency
Office of Research and
Development
Washington DC 20460
EPA/600/R-97/069
August 1997
Ostrava Human
Exposure and Biomarker
Study
11
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EPA/600/R-97/069
August 1997
OSTRAVA HUMAN EXPOSURE
AND BIOMARKER STUDY
by
R. W. Williams, R. R. Watts, T. A. Hartlage, L. Phillips and J. Lewtas
U.S. Environmental Protection Agency, Research Triangle Park, NC, USA
L. Dobias, J. Havrankova and J. Volf
Regional Hygiene Institute, Ostrava, Czech Republic
R. B. Kellogg and R. D. Willis
ManTech Environmental Technology, Inc., Research Triangle Park, NC, USA
J. Novak
Czech Hydrometeorologkal Institute, Prague, Czech Republic
Principal Investigator
R. Williams
Human Studies Division
National Health and Environmental Effects Research Laboratory
Research Triangle Park, NC 27711, USA
National Health and Environmental Effects Research Laboratory
Office of Research and Development
Human Studies Division
Research Triangle Park, NC 27711, USA
Printed on Recycled Paper
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Disclaimer
A portion of the research described in this document has been funded by the United
States Environmental Protection Agency under Contract 68-D50049 to ManTech Environmental
Technology, Inc. It has been subjected to the Agency's peer and administrative review, and it has
been approved for publication as an EPA document. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
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Abstract
A four week repeated measures personal air pollution exposure study was conducted in
the city of Ostrava, Czech Republic, during October and November 1995. Personal exposure
monitoring with 30 participants was conducted to determine the relationship between individual
air paniculate exposures and subsequent biomarkers of exposure and dose to DNA (not reported
here). The 24 hour exposure periods for each individual were divided into day time at the central
work site (KHS-Ostrava) and night time (e.g., at home) away from the central work site. Each
individual was repeatedly monitored one day per week for four weeks. Individual blood and urine
specimens, along with a 24 hour activity log, were collected in addition to fine ambient air
particulate matter during each sampling period. Stationary indoor and outdoor monitoring of fine
ambient air particulate matter at the central site was also conducted. Outdoor ambient monitoring
at several sites across the city of Ostrava was conducted simultaneously (Willis et al., 1997).
Personal exposure concentrations of fine particulate matter (PM2 5), measured during
participant daytime working hours at a central site (KHS-Ostrava), indicated particle exposure
concentrations as high as 474.6 ug/m3. The 30 day daytime average for all study participants was
90.3 ng/m3. The nighttime average fine particle concentration of 43.2 ug/m3 for the same 30
individuals was approximately 50% of the daytime value. These higher exposures during working
hours may result from the work site being situated downwind from industrial emission sources.
This central site was located in an area of Ostrava that had previously been found to have annual
mean PM10 ambient concentrations in excess of the Czech Republic standard of 60 j^g/m3. The
mean 24 hour individual PMZ5 particle exposure in this 30 day study was 57.3 ug/m3.
Carcinogenic PAH concentrations from the 30 day personal sampling showed central
work site daytime ambient concentrations of benz(a)pyrene [B(a)P] that were also higher than
those for the nighttime periods. The daytime B(a)P mean for all participants was 4.7 ng/m3 as
compared to 3.5 ng/m3 for nighttime periods. The overall 24 hour average exposure
concentration for B(a)P was 3.9 ng/m3. Total carcinogenic PAHs were determined by summing
individual concentrations of carcinogenic PAHs. Ambient B(a)P concentrations from personal
monitoring correlated with total carcinogenic PAH concentrations (r^O.77). No correlation was
found for PM2.S particle concentrations and B(a)P concentrations.
PM2 s particle concentrations from indoor stationary monitoring were approximately one-
half of those observed in matched outdoor sampling. Analysis of this same sample set revealed a
high degree of correlation between indoor and outdoor pollution levels using several elements and
individual PAHs. Concentrations of individual species, B(a)P for example, measured outdoors of
the participants work site on various days of the study, were within the same order of magnitude
with those collected by different sampling techniques at three Ostrava ambient monitoring sites.
This would indicate that pollutant concentration data from the primary monitoring sites should
relate to exposure biomarkers for individuals working at the KHS-Ostrava central study site.
This report covers the period from November 1995 to January 1997. Biomarker studies
will be reported at a later date.
in
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Contents
Abstract iii
Figures v
Tables vi
Acknowledgment vii
1. Introduction 1
2. Summary 3
3. Recommendations for Future Work 5
4. Experimental 6
Personal Exposure Monitoring Study Design and Testing Regimen 6
Indoor/Outdoor Study Design 6
Sample Processing 8
Use of Personal Monitors 8
PEM XAD-2 Extraction 9
PEM Filter Extraction and PAH Sample Preparation 9
Indoor/Outdoor Filter Extraction and PAH Sample Preparation 10
XRF Elemental Analysis Procedures 10
PEM and Indoor/Outdoor PAH Analysis Procedures 10
Biological Sample Processing and Analysis 11
5. Results and Discussion 12
PEM and Biomarker Sample Collection 12
PEMPM25 Mass Analysis 12
PEM PM2^5 PAH Analysis 13
Indoor/Outdoor PM2 5 Mass and PAH Analysis 16
Indoor/Outdoor PM2 5 XRF Elemental Analysis 17
References , 19
IV
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age
Figures
1. Fine Paniculate Matter Personal Monitor 20
2-11. PM25 Mass Concentrations from Personal Monitoring 21
12-15 PM2.5B(a)P Concentrations from Personal Monitoring 31
16-19. PM 2.5 Total Carcinogenic PAH Concentrations from Personal Monitoring 35
20. Correlation of Personal Monitoring PM 25 B(a)P and Total Carcinogenic PAH 39
21. Correlation of Personal Monitoring PM 2 5 Mass and B(a)P 40
22-31. PM 25 Mass and B(a)P Concentrations Depicted by Residence Locations 41
32. Daily Variation of Indoor and Outdoor PM 25 Mass Concentration at KHS-Ostrava
from Stationary Monitoring 46
33. Daily Variation of B(a)P and Total Carcinogenic PAH Concentration at KHS-Ostrava
From Stationary Monitoring 47
34. Daily Variation of B(a)P to Lead Ratio at KHS-Ostrava From Stationary Monitoring 48
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Tables
Table
Page
1. Personal Monitoring andBiomarker Study Design 49
2. HPLC Conditions for PAH Analysis 50
3. Collection Results of Environmental and Biological Samples 51
4. Results from Fine Particulate Matter Personal Monitoring 53
5. Results from PAH Personal Monitoring 54
6. Total Carcinogens Measurements from Personal Monitoring 55
7. Indoor/Outdoor Sample Collection Results 56
8. Comparison of Regional Outdoors B(a)P Concentration 57
9. Elemental Analysis Results from Indoor Monitoring 58
10. Elemental Analysis Results from Outdoor Monitoring 59
11. Correlation of Paired Elemental Species from Indoor and Outdoor Monitoring 60
12. Indoor/Outdoor Metal Concentration Ratios 61
VI
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Acknowledgment
The authors would like to thank Anna Phillips and Jane Metcalf of the U.S.
Environmental Protection Agency (USEPA) for their administrative and financial support
throughout the scope of the study. The authors also acknowledge the contributions of J. Kusova,
M. Lorkova, R. Rakusova, M. Skopalova, J. Tvrda, M. Adamcik, and J. Lvoncikova from KHS-
Ostrava for their contribution in the collection of environmental and biomarker samples described
in this report; James Scott (USEPA) for assisting in PAH filter extraction; Dina Schreinmachers
(USEPA), Debra Walsh (USEPA) , Debra Costa (UNC-CH), and for their technical review of
the document; Robert Stevens (Florida Department of Environmental Protection) and Rebecca
Calderon (USEPA) for their editorial and technical comments.
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Section 1
Introduction
A collaborative research program involving the Czech Ministry of Environment, the Czech
Institute of Hygiene (KHS-Ostrava) and the U.S. Environmental Protection Agency (EPA) has
been ongoing since 1992. The objective of this program is to reduce the uncertainties in the risk
assessment of polycyclic organic matter (POM) and polynuclear aromatic hydrocarbons (PAH)
adsorbed to respirable particles through research on human exposure, biomarkers of exposure,
dose, susceptibility and cancer risk. The best human cancer risk data is based on studies of coke
oven workers, therefore Ostrava was selected for these studies since the town includes several
large active coke ovens. Previous studies conducted as part of this research program have
focused on the highest human exposures found in coke oven workers. Results from these studies
show that coke oven workers are exposed to extremely high and variable levels of fine particulate
matter (30-17,000 ug/m3) and polynuclear aromatic hydrocarbons [benz(a)pyrene 6-42,000
ng/m3]. Supporting data from biomarker studies of these same workers revealed that at high
concentrations of environmental exposures the formation of DNA adducts may be nonlinear
(Lewtas et al., in press). Other studies have been conducted in the Czech Republic on residents
and workers exposed to much lower concentrations of particles and PAH than those from coke
oven workers (Watts et al., 1994; Binkova et al., 1995).
The primary objective of this study is to improve our understanding of the relationship
between ambient and personal exposures in Ostrava for a typical population not occupationally
exposed to coke oven emissions. The PAH exposures were assumed to be substantially lower
than observed for coke oven workers and higher than previously reported for ambient exposures
in Northern Bohemia. Furthermore, the study was designed to evaluate variability of exposure
and dose both within and between individuals over a four week period. This study was conducted
through a collaboration between the US EPA Office of Research and Development National
Laboratories (National Exposure Research Laboratory, NERL and National Health and
Environmental Effects Research Laboratory, NHEERL), Czech Hydrometeorological Institute
(CHMI), and the Ostrava Regional Institute of Hygiene (KHS-Ostrava). The Ostrava Exposure
Monitoring Project, also known as Project Silesia, involved the collection of a range of
continuous real-time as well as time-averaged environmental pollutant measurements. Three
stationary monitoring platforms located strategically around three (3) major coke ovens in
Ostrava, Czech Republic were utilized to collect ambient pollutant concentrations of PAH,
volatile organic compounds, metals, volatile carbon, coarse and fine particulate mass, SO2,
NO/NO2/NOX, and CO. Meterological parameters at the sites were also measured.
The personal exposure and biomarker component of this study, reported in part here, was
conducted with volunteers from KHS-Ostrava over a 4 week period (The Ostrava Human
Exposure and Biomarker Study). KHS-Ostrava is located within the area bracketed by the
stationary monitoring platforms. Daytime and nighttime PM2 5 measurements were performed on
each volunteer and PAH analysis conducted upon the collected particulate matter. Blood and
urine specimens were collected from these same 30 individuals for exposure, dose, and
susceptibility biomarker analysis (studies in progress). Volunteers were selected to represent a
range of distribution of possible nighttime (home) exposures based on the proximity of residences
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to the known pollutant point sources (e.g., coke ovens). Individual PAH exposures within the 4
week study were expected to vary due to changing meteorological conditions. This variation in
exposure across the 4 repeated sampling periods will be used to evaluate within and between
individual variability in both personal exposure and biomarkers of exposure and dose.
A second component of the Ostrava Health Study investigated the relationship between
indoor and outdoor concentrations of PM2.5 and select subspecies. Matched fine particulate
matter samplers were operated at KHS-Ostrava and operated for a 2 week period.
Concentrations of PM2.S mass, PAH, and selected elemental species from collected samples were
determined during the event.
This report details the study design, sampling and chemical analysis of the personal of
personal exposure samples, and collection of the human samples for biomarker studies. Individual
as well as average exposures to environmental pollutants are reported here. Comparisons are
made between daytime and nighttime personal exposures relating to various geographical
locations within the city of Ostrava, Czech Republic. Biomarker studies are in progress and will
be reported at a later date. Correlation of outdoor and indoor pollutant concentrations of select
species is described. Recommendations for future studies are also provided.
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Section!
Summary
The principal objectives of the Ostrava human exposure and biomarker study were the
following:
1. To improve our understanding of the relationship between ambient and personal exposures
in Ostrava for a typical population not occupationally exposed to coke oven emissions.
2. To determine individual and population exposures to fine particulate matter (PM2.S) and
the associated particle-bound polynuclear aromatic hydrocarbons (PAHs).
3. To determine the relationship between indoor and outdoor exposures for this population.
4. To evaluate the relationship between the coke oven source of emissions and personal
exposure.
5. To evaluate variability of exposure and dose both within and between individuals over a
four week period.
This report provides the detailed sampling and chemical analysis report for the personal
exposure and indoor/outdoor component of the Ostrava 30 day study. A second study performed
concurrent with this study and not reported here (R. Willis et al., 1997), describes the ambient
exposure concentrations across the town of Ostrava over the same 30 day period. The biomarker
studies are in progress and will be reported separately at a later time.
An investigation of the relationship between outdoor and indoor air particle concentrations
at the participants work site (KHS-Ostrava) was conducted simultaneously with the personal
monitoring biomarker exposure assessment study. Results of the studies reported here are
summarized below:
• Planned collection of biological and environmental samples as part of the associated health
study was successful (99, 85% respectively). A total of 30 volunteers from diverse
occupations within the KHS facility participated in the health study over a period of 4
weeks. These participants included nurses, physicians, biologists, tradesmen, etc. All
were nonsmokers with no known occupational exposure to PAHs. Their residences were
located in geographically diverse areas of Ostrava.
• Personal exposure monitoring (PEM) for fine particle (PM2 5) concentrations ranged from
14.5-474 ug/m3. Daytime concentrations averaged 90 ng/m3 over the 4 week period with
nighttime concentrations averaging 43 ug/m3. Residential particle exposure
concentrations were therefore approximately one-half of daytime concentrations at the
KHS facility. The mean 24 hour exposure for the entire study was 57 ng/m3. Significant
individual variations in particle exposures were observed and explained by 24 hour
personal activity logs.
• Total carcinogenic PAH concentrations from individual personal air monitoring were
found to vary between 0.4-393 ng/m3 and averages for all participants over the 4 week
study ranged from 17-45 ng/m3. Concentration of benzo(a)pyrene [B(a)P], as well as
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other carcinogenic PAHs, were higher in daytime samples collected from the participants
at the central work site (KHS-Ostrava) compared to those from nighttime samples from
individual residences located throughout the city (4.7 versus 3.5 ng/m3 respectively). The
average 24 hour exposure to B(a)P was 3.9 ng/m3. B(a)P concentrations correlated with
total carcinogenic PAH but did not correlate with personal fine particle concentrations.
Results from stationary indoor and outdoor monitors at the participants work site (KHS in
central Ostrava) showed correlations for particle concentrations and for B(a)P
concentrations. X-ray fluorescence (XRF) analysis of indoor and outdoor particles
revealed significant concentrations for the elements like barium, zinc, iron, copper,
bromine, titanium, manganese and lead among others. The ratios of B(a)P to lead (lead is
a tracer for emissions from gasoline powered vehicles) indicates significant PAH sources
other than these vehicle emissions.
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Section 3
Recommendations for Future Work
Complete the analysis of select biomarker samples. This involves work earlier proposed
by the research staff at KHS-Ostrava as well as those of NHEERL. Coordination of
efforts between the respective laboratories should occur to focus efforts upon prime
samples of interest.
Personal exposure data should be integrated with both ambient exposure data and
individual biomarker concentrations when these data are available. This would include
DNA-adduct, albumin adducts or other assays available to investigate the question of
individual variation in exposure-biomarker relationship.
Perform matched indoor and outdoor exposure monitoring at various Ostrava locations
and building types to further investigate fine particle infiltration.
Initiate epidemiological studies relating ambient PM2 5 concentrations to physiological and
biochemical responses in select populations. Variations in PM2 5 mass concentrations
among study participants and during the course of the study offer an excellent opportunity
to investigate presumed physiological health effects resulting from fluctuating PM2 5 mass
concentrations.
Biomarker susceptibility profiles should be performed upon each volunteer involved in the
study utilizing metabolic genotyping techniques.
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Section 4
Experimental
Personal Exposure Monitoring Study Design and Testing Regimen
A personal exposure monitoring component of the project was conducted using 30
volunteers from the Ostrava Institute of Hygiene (KHS) during October 16th- November 9th
1995. These were non-smokers and non-occupationally exposed adults (age 30-50 years old)
who received no compensation for their involvement. The 30 volunteers (12 male, 18 female)
were divided into two 15 member groups to permit the KHS Department of Genetic Toxicology a
reasonable amount of time to perform ambient personal monitoring as well as collect and process
human biological specimens during each week of the study (a total of 4 weeks). The test subjects
were issued one flow-calibrated personal exposure monitor (PEM) at approximately 8 am on
Monday (group 1) or Thursday (group 2) of each week with instructions as to its operation. The
PEMs were placed on each volunteer so that the inlets of the units were within their respective
breathing zone. Each volunteer was then given two vessels for collection of urine with
instructions to collect their next void specimen and return it to the study coordinators
(refrigerated when immediate return was not possible). Volunteers were instructed to collect
their first void of the next morning and bring it with them to the study center. Each volunteer
returned to the study center at approximately 4:00 pm on the day the PEM was first issued where
the existing PEM was replaced with a new PEM. This changing of PEMs was conducted so that
PM2.5 measurements could be obtained from each group of volunteers during their work hours
(hereafter called daytime samples) at the central site (KHS-Ostrava) as well as from their
respective non-work residences and habits (hereafter called nighttime samples).
Volunteers returned to the study center on the following morning with a freshly collected
urine specimen. Personal monitors were recovered from each individual by the study staff who
then administered a questionnaire regarding the past 24 hours (e.g., type of residence, home
location, work and home activities, passive smoke exposure). A 20 ml blood specimen was then
collected from each respondent (20 ml via an EDTA-treated vacutainer tube). Volunteers were
then instructed about returning for the next sampling period (one-24 hour period for four
consecutive weeks). Individuals were placed upon either a Monday-Tuesday or a Thursday-
Friday schedule at initiation of the study with no changes allowed during the four weeks. A
summary of planned environmental and biological specimen collection is presented in Table 1.
Indoor/Outdoor Study Design
Experiments were designed to investigate the relationship between indoor and outdoor air
at KHS-Ostrava. The KHS site was selected based upon criteria such as availability of study
personnel to operate the samplers, the presence of an existing monitoring platform (with weather
protection) and the fact that KHS-Ostrava was in a geographically acceptable location relative to
the three NERL/CHMI stationary monitoring sites incorporated into Project Silesia.
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One cyclone-equipped PM2 5 fine paniculate matter sampler (University Research
Glassware, Carrboro, NC) was placed at the 2 meter level within an unoccupied office on the
ground level of the KHS's main building (hereafter called indoors). This site was co-selected by
KHS and EPA investigators on the basis of noise concerns about positioning the accompanying
101/min air sampling pump, the relative infrequency of foot traffic into the room and the fact that
it was representative of offices found throughout the facility (furnishings). The selected office
was separated from a main automotive thoroughfare by a distance of approximately 50 meters
with approximately a 60 space employee parking lot located within 10 meters of the office
windows. Room temperature was controlled by adjusting radiator controls within the office and
by the opening and closing of large windows. At times throughout the study, wind originating
outside was easily detectable in the vicinity of the indoor fine particle sampler. This was without
doubt the result of air movement passing through the open windows.
A second URG PM2 5 fine particulate matter sampler was placed at an outdoor particulate
monitoring platform located behind the Department of Genetic Toxicology at an inlet height of 2
meters. Co-located at this site were other KHS-Ostrava particulate monitoring instruments not
related to this study. This site was buffered from automotive traffic by a 25 meter wide tree-
covered park on one side with a distance of 10 meters separating the monitoring platform from
the wall of an adjacent KHS building.
Stationary indoor and outdoor fine particulate matter sampling was performed during the
period of October 27th-November 9th to coincide with personal and primary stationary site
monitoring that was underway in the overall study. Sampling was performed by placement of a
single tared 47 mm Teflon (Gelman) Teflon filter within the filter pack of each sampler at
approximately 8:00 am each day. Each sampler's pump was then calibrated to achieve a flow rate
of 10 ± 0.1 L/min. Filters were recovered from each sampler after 24 hours and exchanged with
fresh filters. Total collected flow (m3) was determined for each sampling period by direct
measurement using an in-line dry gas meter (Schlumberger-Gallas 2000). Collected filters were
returned to CHMI laboratories where mass loadings were determined following 24 hour
equilibration at constant temperature and humidity.
Area air monitoring was conducted at three monitoring platforms operated by the Czech
Hydrometeorological Institute, the Regional Hygiene Institute in Ostrava and NERL (EPA).
These sites were located in Privoz, Radvanice, and Zabreh districts of Ostrava. Each was chosen
due to their proximity to large, medium and small ambient air pollution point sources and to their
respective locations that triangulated the city as a whole. The platforms were operated in a time
period to coincide with the personal exposure study. Species monitored included PAH, volatile
organic compounds, metals, volatilizable and elemental carbon, coarse and fine particulate mass,
SO2, NO/NO2/NOX, and CO. Meterological parameters at the sites were also measured.
Detailed results from this monitoring is reported elsewhere (R. Willis et al., 1997).
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Sample Processing
The study staff returned all collected environmental and biological samples to laboratories
within the Department of Genetic Toxicology where sample processing and recovery was
initiated. Each PEM was audited for a final flow rate which was averaged with the initial
calibration flow to yield an average used in calculation of the total collected air volume (the
product of the elapsed run time and the average flow rate). Pre-tared Teflon- impregnated glass
fiber (TIGF) filters were removed from each PEM using clean stainless steel tweezers and placed
within a constant relative humidity chamber for 24 hours to achieve hygroscopic equilibration.
PM2 5 mass loading was then determined by reweighing each filter using a microbalance sensitive
to O.Olmg. Weighed filters were then placed within individual storage vials. XAD-2, contained
within the vapor-phase collection module of each sampler, was decanted into separate glass
storage vials and sealed with Teflon-lined screw caps. Filter and XAD-2 samples were stored at
-40°C awaiting either KHS analysis or transport to US EPA laboratories.
Aliquots from each collected urine sample were transferred by the study staff into plastic
vials for future or possible analysis: creatinine (Czech), metabolic genotyping (Czech) 1-
hydroxypyrene(Czech), mutagenicity (Czech), cotinine (EPA), metabolic genotyping (EPA), PAH
metabolites (EPA), DNA and albumin adducts (EPA). Storage at -40°C was utilized prior to any
analysis.
Blood specimens were processed immediately after their collection by the staff using
standard KHS clinical procedures for recovery of serum, white and red blood cells. Components
of whole blood were processed and ultimately transferred to plastic tubes for storage at -40°C
until analysis by KHS-Ostrava investigators or transport to US EPA laboratories.
Use of Personal Exposure Monitors (PEMs)
This study involved use of a PM2.5 size-selective impactor to allow for the collection of
respirable suspended particulate (RSP). The device selected was one designed by the US
Environmental Protection Agency as reported in detail by (Williams et al., 1992; Watts et al.,
1994). A depiction of the device is presented in Figure 1. In summary, the PEM consists of a
Teflon coated aluminum elutriator operated at a face velocity of 5.1 cm/sec which when
connected to a specially designed impactor assembly, focuses particles having an aerodynamic
diameter of >2.5 um onto the impactor surface. The impactor is a removable 4.5 mm
borosilicate disc coated with 6 ul of 1:1 (v/v) 400 polyethylene glycol:600 polyethylene glycol.
Non-impacted particles (ie, 0.5 um. Particle-denuded air was then channeled
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into an attached Teflon resin cartridge. The cartridge has an interior void dimension of 1 X 5 cm
(width X depth) with a total volume of 3.9 cm3 available for use. A total mass of 2-2.5 g (dry
weight) of 20/40 mesh size styrene-divinylbenzene, having the trade name of XAD-2 (Rohm &
Haas, USA) was utilized to collect vapor-phase components in the airstream.
Flow was brought into and through the above connected assemblies (inlet, filter pack, and
vapor phase cartridge) by means of a battery powered personal air sampling pump. The Shibata
MP-15CF was selected for it's ability to run continuously for 24 hours using a single set of
alkaline batteries (8/pump) as well as it's flow constant capabilities. Each sampling pump was
calibrated to have a flow rate of 1.5-1.7 1/min after new batteries had been installed and allowed
to discharge for 0.5 hours while attached to a blank PEM. Calibration was performed by
configuring the flow through an EPA primary standard calibrated flowmeter while a complete
PEM (inlet, filter and XAD-2 cartridge) prepared for field use was attached.
PEM XAD-2 Extraction
Chemists from KHS-Ostrava had the responsibility to extract all XAD-2 samples
associated with the personal monitoring. The proposed technique involved the addition of 25 ml
of high purity dichloromethane into each borosilicate vial containing recovered XAD-2. The
contents of each vial was to be thoroughly vortexed for 10 minutes using a mechanical process.
At that time, the extract from each vial was to be decanted into individual, solvent cleaned,
borosilicate tubes capable of holding 100 ml of volume. A fresh 25 ml aliquot of dichloromethane
was to be added to the original sample vials and the vortex process repeated for another 10
minutes. Recovery of this extract with quantitative transfer would complete the extraction. As of
this date, the extraction and subsequent PAH analysis of XAD-2 samples associated from
personal monitoring has not been completed by KHS scientists.
PEM Filter Extraction and PAH Sample Preparation
TIGF filters from each PEM were transferred to US EPA laboratories for extraction and
PAH analysis. Filters were removed from their individual storage containers and singularly placed
within dichloromethane cleaned 4-dram borosilicate vials. A 20 ml aliquot of dichloromethane
(DCM) was added to each vial followed by sonication extraction for 10 min (25°C). Extract from
each vial was decanted into individual 100 ml borosilicate culture tubes. The above extraction
process was repeated a total of 3 times. Quantitative transfer of the final extract was completed
by rinsing the filter and extraction vial with 3 X 5 ml volumes of DCM and transferring this to the
collection tube.
Extracts were then concentrated down to a volume of approximately 5 ml using nitrogen
evaporation (35°C). Concentrates were then quantitatively transferred into borosilicate syringes
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equipped with 0.45 micron Teflon filters. Filtrates were collected in 15 ml borosilicate conical
centrifuge tubes where they were subsequently placed under nitrogen evaporation (35°C) for
concentration/solvent exchange purposes. Concentration was intermittently stopped to permit
vortex mixing (1 minute) as volumes approached 5 and 1 ml. Solvent exchange was completed
by nitrogen evaporation of the last 1 ml volume of DCM residing in each centrifuge tube with it's
immediate replacement with 0.5 ml of HPLC-grade acetonitrile. Vortexing of each solvent-
exchanged sample was then performed to ensure displacement/solvation of PAH residues from
the interior walls of the vessels. DCM cleaned borosilicate pipets were utilized to transfer 200 ul
of each extract prepared for HPLC analysis into individual borosilicate autosampler vials (amber
with inserts). Autosampler vials awaiting analysis were stored at -30°C until HPLC was
performed.
Indoor/Outdoor Filter Extraction and PAH Sample Preparation
The outside retaining (handling) ring of each Teflo filter was removed using stainless steel
scissors because of it's incapability with the extraction solvent (DCM). Each filter was then
individually placed into DCM cleaned 4 dram borosilicate vial for extraction and workup as
immediately described above for PEM filters.
XRF Elemental Analysis Procedures
Multi-elemental energy dispersive X-ray fluorescence (XRF) analysis was performed by
US EPA contractors (ManTech Environmental) using EPA-approved procedures. The instrument
utilized was custom designed by Lawrence Berkeley Laboratory and has features specialized for
the analysis of environmental pollutants collected upon filter media. The excitation tube is
operated in a pulsed mode with a 83 usec off-time immediately after x-ray detection. A
cryogenically cooled lithium-drifted silicon detector allows for optimized collection of x-rays.
Four secondary fluorescent targets (Ti, Co, Mo, and Sm) are sequentially excited by the X-ray
tube to optimize sensitivity. Both vacuum-deposited metal film as well as polymer film standards
are used in the calibration of the instrument. Standard reference materials (NIST#1832 and
#1833) are measured before and after each analytical run to validate daily calibration. An
accuracy of ± 10% has been established for the methodology.
PEM and Indoor/Outdoor PAH Analysis Procedures
PAHs were analyzed using analysis high performance liquid chromatography (HPLC)
coupled with time-programmable fluorescence detection. The basis behind the techniques have
previously been reported (Williams et al, 1994, Watts et al, 1994). In essence, HPLC is utilized
to resolve complex environmental extracts containing PAHs into individual peaks where
optimized fluorescence excitation and emission wavelengths are utilized to increase both analyte
sensitivity and specificity. Duplicate 20 ul aliquots of each solvent exchanged extract were
automatically injected into an HPLC configured for PAH analysis. This system consisted of a
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Varian Star (v. 4.0) data station connected to a Varian 9095 autosampler, a Waters 680 gradient
controller and one Waters 510 pump. A 25 cm X 4.6 mm Supelco LC-PAH column was utilized
to achieve chromatographic resolution of the PAHs of interest. A 40°C isocratic solvent
composition of helium sparged 90:10 (v/v) acetonitrile: water flowing at 1.5 ml/min eluted
extract components into a Perkin Elmer LS40 fluorescence detector. The detector was operated
at conditions to achieve acceptable analyte sensitivity and specificity as listed in Table 2.
Multipoint calibration curves for each PAH were established for each 24 hour
chromatographic run sequence (3X4 concentration levels). Solvent and field filter blanks were
run throughout each sequence to document system and method contamination. Raw PAH
retention and peak area data was analyzed using the Varian Star (4.0 software) to obtain
summarized PAH concentrations. Summarized PAH data was then manually transcribed into
spreadsheets (Excel v 5.0) where sample collection information was incorporated to yield
individual and total ambient PAH concentration level. Graphic representations of PAH and
PM2 5 fine paniculate mass data from the study were prepared by manipulation of the spreadsheets
discussed above (Excel v 5.0).
Biological Sample Processing and Analysis
The analysis of biological specimens will not begin until the spring of 1997. This is due to
the desire of Czech and US EPA researchers to define subgroups of those participating in the
study for an intense investigation into the variability of biomarkers as they relate to ambient
exposure. It is expected that results from the analyses listed below will be completed or initiated
in 1997. Details of each, as well as results, will be reported at the conclusion of the biomarker
studies at a later time.
Pending Biomarker Study Analyses
Creatinine -Pending reporting by KHS-Ostrava
Metabolic genotyping-Pending analysis and reporting by KHS-Ostrava
1-hydroxypyrene-Pending reporting by KHS-Ostrava
Mutagenicity-Pending reporting by KHS-Ostrava
Cotinine-Pending analysis and reporting by US EPA
Metabolic genotyping-Pending analysis and reporting by US EPA
PAH metabolites-Pending analysis and reporting by US EPA
DNA and albumin adducts-Pending analysis and reporting by US EPA
11
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Section 5
Results and Discussion
PEM and Biomarker Sample Collection
The successful collection of biological and environmental specimens associated with the
health study is depicted in Table 3. Nearly 100% of the samples desired in the health study were
collected. Two individuals had illness or hospitalizations that temporarily removed them from the
project (K>#2,28) but all other subjects completed all required collections (environmental or
biological). Collection of biological samples was without complications due to the concerted
effort of KHS-Ostrava investigators. Personal monitoring was somewhat more difficult in that
while an attempt to collect every sample was exerted some equipment failure was noted. PEM air
sampling pump failure was often the result of suspect alkaline batteries. A total of 15% (36/240)
of the PEM collections were removed from the data base after US EPA quality assurance
procedures because of flow rate fluctuations exceeding 20% of initial set point values or
inappropriate flow rate settings during sampling. Missing values observed for data points for
individuals in figures discussed throughout this results section (PM2 5 mass, PAH, carcinogenic
PAH) are the result of these quality assurance procedures.
While an effort to have 50/50 participation of male/female in the study was desired, it was
not found possible. The final study population reflected a greater participation by female
volunteers at KHS-Ostrava (18 out of 30). Volunteers expressed few complaints about either
wearing the PEM or providing blood and urine specimens. This was attributed to the great
enthusiasm displayed by Czech investigators leading the study at KHS-Ostrava and the sincere
interest of the volunteers in participating. No "drop-outs" from among the volunteers occurred
over the course of the 4 week study.
PEM PM2 5 Mass Analysis
Individual, average and total exposures to PM2 5 from PEM sampling is shown in Figures
2-11. Each of the figures is broken down to specify collection period, volunteer ID (or grouping),
respirable particulate matter (RSP), concentration in ug/m3, day and nighttime sampling. Note
that volunteers 1-15 represent PM25 Monday-Tuesday sample collections while ID numbers 16-
30 represent Thursday-Friday collections. Thus, there may be notable differences in data from the
two groups as influenced by ambient weather and pollution episodes changing during each of the
4 weeks. PM2.5 mass exposure for the 30 participants is summarized in Table 4. A west-
southwest wind pattern dominated weeks 1-3 while week 4 had a weather pattern where winds
fluctuated from the southwest/north-northwest. Summarization of daytime and nighttime
exposures are presented in Figures 6 and 7.
The summary listed on Table 4, indicates that daytime concentrations of RSP greatly
exceeded that of nighttime periods. The overall daytime mean RSP concentration for all
12
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participants was determined to be statistically higher (PO.0001, a= 0.05). This was somewhat
expected due to the fact that daytime sampling was centered around KHS-Ostrava which is
located near operating coke oven and steel work facilities (Sverma and Vitkovice) while
nighttime sampling was influenced by a wide distribution of homes throughout Ostrava. Daytime
sampling ranged from 14.5-474.6 ng/m3 over the course of 4 weeks with an average of 90.3
Hg/m3 observed. This average was highly influenced by volunteers like #2, 14, 16, 29 and 30 who
often had daytime exposures 2-5 fold higher in comparison to other KHS-Ostrava staffers.
Personal survey information was reviewed to determined what conditions were prevalent that
separated these and similar individuals in terms of their RSP exposures. A cursory investigation
determined that exposure to pollutants from passive cigarettes, cooking aerosols, machinery, or in
the case of volunteer #30, fine wood dust might account for the elevated exposures. A more
sophisticated analysis will have to be performed to fully investigate the findings. RSP
concentrations were found to fluctuate during the four weeks with week 4 having an appreciably
lower average concentration than that encountered during weeks 1-3 (35 ug/m3). This was
probably the result of changing wind conditions discussed above.
Results from nighttime RSP collections revealed that while concentrations fluctuated
between the 30 volunteers, they were not of the same magnitude as that observed in the daytime
central site data (KHS-Ostrava). Rarely was a 2 fold difference observed during a given week
between individual exposures regardless of where they lived within the city. Nighttime
concentrations ranged from 5.1-281.8 ug/m3 during the entire study with an overall average of
43.2 ug/m3. Averages from individual weeks ranged from 22.3 ng/m3 (week 4) to 58.9 ug/m3
(week 3).
Calculations were performed that summarized each individual's total 24 hour RSP
exposure (Figures 8-11). Pooling all 30 individuals/week resulted in a range of 27.6-77.8 ug/m3
weekly. The overall 4 week average was 57.3 ug/m3. Week 4 was found to have 24 hour
ambient RSP concentrations that would be typical of one relatively free from commonly
encountered industrial/residential emission sources (27.6 ug/m3) . It should be kept in mind that
northern wind patterns dominated meteorological conditions during the first half of week 4 as
reported by CHMI platform monitoring not detailed in this report. This in effect would drastically
alter the normal industrial-influenced RSP fallout in Ostrava.
PEM PM2 5 PAH Analysis
PAH analysis from the individual PEMs indicated detectable levels of carcinogenic PAHs
were present in most of the collected samples, especially those collected at KHS-Ostrava.
Measurements were performed for the IARC listed animal carcinogenic PAHs detailed in Table 2.
Pyrene was measured but is not a listed carcinogen and was not included in total carcinogenic
PAH levels described here. Benz(a)anthracene, benz(a)pyrene, benzo(ghi)perylene, and
indeno(cd)pyrene were often found to be the dominant species (by concentration) of those
investigated. Overall detectability of PAHs was hindered by having two sampling periods for
13
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each 24 hours (8- hour daytime, 16- hour nighttime). This division reduced the total sample
available for analyte determination as compared to normal 24 hour integration, nevertheless,
quantification was possible within quality assurance margins.
Benz(a)pyrene concentrations determined from PEM analysis are presented in Figures 12-
15. Daytime versus nighttime sample collection periods are depicted in the figures for each week
of the study. A summary of this data is shown in Table 5. Daytime B(a)P concentrations were
found to range from 0.7-22.0 ng/m3 during the study with a 4-week average of 4.7 ng/m3. There
were some individual variation in B(a)P concentrations observed for daytime sample collections,
generally within 2-5 fold of the overall high-low extremes. Monday-Tuesday versus Thursday-
Friday sample collections also revealed observable daytime B(a)P concentration variations.
Daytime B(a)P concentration patterns followed those observed with RSP determinations
with the exception of measurements during week 2 (ie, daytime having higher concentrations than
nights). During this week, average nighttime B(a)P concentrations were nearly twice the daytime
values (6.5 vs 3.6 ng/m3) respectively. Nighttime values represent exposures during non-work
hours and would typically, reflect travel and home indoor conditions. An explanation for this
atypical finding has not been proposed at this time. Nighttime B(a)P concentrations were found
to range from 0.3-22.0 ng/m3 during the 4 weeks. Average weekly concentrations ranged from
1.1-6.5 ng/m3 with an overall monthly average of 3.5 ng/m3. The overall daytime mean B(a)P
concentration for all participants was determined to be statistically higher in comparison to
nighttime exposures (PO.0229, a= 0.05).
Total B(a)P exposure during the 24 hour sample collection period was calculated for each
participant as the sum of daytime and nighttime exposures. Weather conditions were probably
responsible for the low 24 hour average exposure concentration observed for week 4 (2.5 ng/m3).
This week also had low RSP values (overall average <30 ug/m3) suggesting that PAH exposures
observed during this week are probably background levels contributed by mobile source or
similar urban emissions with only minor influences from industrial sources (e.g., coke oven
batteries). An overall 4 week 24 hour average of 3.9 ng/m3 of B(a)P was observed from
summarizing exposure from all individuals. Week 2 collections were found to have the highest
24 hour totals (6.0 ng/m3), again heavily influenced by nighttime exposures.
Individual carcinogenic PAH concentrations, the sum of 8 I ARC listed animal
carcinogens, were utilized to obtain a value of total carcinogenic PAH exposure. Graphic
depiction of this data is shown in Figures 16-19. Summary of the individual exposures is
presented in Table 6. Variability was observed between given individuals and collection periods
which followed the pattern observed in both the fine particulate matter and B(a)P measurements.
An exposure range of 0.4-393.2 ng/m3 for daytime sample collections occurred over the 4 week
period. Week 1 had the highest overall daytime average of 68.6 ng/m3 and week 4 exposures
had the lowest overall daytime average of only 18.8 ng/m3. The standard deviation calculated
between individual total carcinogen exposures within each week of sampling revealed a high
14
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degree of fluctuation (overall 4 week standard deviation average of 21.9 ng/m3). The 4 week
overall daytime average for total carcinogenic PAH exposure was calculated to be 36.6 ng/m3.
Nighttime total carcinogen exposures for week 2 followed the pattern established in
analysis of the B(a)P data, i.e., higher nighttime than daytime exposures (average of 46.7 ng/m3).
A range of 0.5-226.6 ng/m3 was revealed over all nightime personal monitoring during the 4
weeks with an overall average of 25.8 ng/m3 calculated. Review of the average weekly exposures
indicated that weeks 2-3 had approximately 3-4 fold higher ambient nighttime concentrations in
comparison to weeks 1 and 4 . Cumulative total carcinogen (24 hour) exposures were calculated
for each individual and averaged for each week. The average 24 hour exposure ranged from 17.4
ng/m3 (week 4) to 44.7 ng/m3 (week 2) with an overall average of 29.0 ng/m3. The overall
daytime mean total carcinogenic PAH concentration for all participants was determined to be
statistically higher in comparison to nighttime exposures (PO.0489, a= 0.05).
Comparison of exposure data collected from all 4 weeks of the personal monitoring
revealed B(a)P correlations of R2=0.7706 in relation to total carcinogenic PAH concentrations.
This is graphically depicted in Figure 20. This correlation is important in that B(a)P levels may
be used as a significant indicator of overall PAH exposures in future studies when conditions
similar to those encountered here are present. Cumulative RSP and B(a)P concentrations from
the entire study failed to correlate as graphically depicted in Figure 21. This result would
indicate that RSP determinations alone would not be an acceptable indicator of personal ambient
exposure to PAHs, including those that are carcinogenic in this study. This finding is consistent
with the "personal cloud" concept. RSP data from personal monitoring often fails to correlate
well with stationary monitoring because of the human interaction with dust and dust-laden
surfaces that stationary monitoring does not take into account. A more thorough statistical
evaluation of individual as well as total carcinogenic PAH concentrations with respect to RSP
findings will be necessary to fully understand their relationship.
Because the 30 volunteers involved in the personal monitoring lived throughout different
parts of Ostrava, data from their nighttime collections were investigated as to RSP and B(a)P
concentrations and either Monday-Tuesday or Thursday-Friday collection periods.. Ostrava was
geographically broken down into three sections based approximately upon distribution of benzene
soluble organic (BSO) concentration data determined in 1993-95 by KHS-Ostrava and other
Czech Republic Ministries (Report No 5-Silesia Environmental Health Report, 1995). This
distribution basically divides the western half of the city into one part (group#l) with the
remaining eastern side divided horizontically into two portions at approximately the center of
Ostrava (northeastern distribution was labeled group #2, southeastern distribution labeled group
#3). Groups 1,2,3 were broken down into participants numbering 10,11, and 9 respectively.
Pollutant concentrations of all individuals living within the specified group were averaged.
Average pollutant concentrations, including the location of individual homes, dominant wind
patterns (seen as arrows within the maps), coke oven and monitoring sites are shown in Figures
22-31.
15
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Review of this spatial distribution of ambient nighttime RSP and PAH concentrations
would indicate that when west/southwest or westerly winds dominate meteorological conditions,
individuals living within group #1 experienced the lowest average B(a)P exposure in relation to
the other groups. Averages from all 4 weeks revealed that group #1 had overall B(a)P
concentrations ranging from 2.60-3.01 ng/m3 (Monday and Thursday, respectively) with group
#2 and #3 experiencing average monthly concentrations of 3.94^4.84 and 3.63-2.79 ng/m3 B(a)P
(Monday and Thursday, respectively). Review of this same data would support the concept
presented in the 1995 Czech report on BSO data that residents living within the geographical
area represented by Group #2 (central to east-north/northeastern Ostrava) are exposed to higher
overall B(a)P concentrations in comparison to other locations (Vit et al, 1995). Statistical analysis
conducted on all nighttime exposure measurements relative to the three groups indicated that
group#3 participants experienced the highest overall RSP exposures for the 30 day study (93.2
ug/m3) but that there was not a significant difference between any of the group means (P>0.6699,
a= 0.05). Comparison of overall B(a)P exposures between the groups for all nighttime
measurements failed to detect differences in mean values (P>0.1360, a= 0.05) with group#2
observed to average 4.46 ng/m3. It should be noted that locations of major industrial pollution
sources, like coke ovens, are positioned so that the dominant wind pattern could potentially carry
PAH-rich emissions into the upper right half of Ostrava (Group #2 in this study).
Indoor/Outdoor PM2.5 Mass and PAH Analysis
Sample collection information from indoor/outdoor monitoring at the KHS-Ostrava is
presented in Table 7. Indoor RSP concentrations were calculated to average 56.2 % of those
determined from outdoor measurements after samples voided for quality assurance reasons (filter
or equipment failure) were removed from the data set. Indoor concentrations ranged from 8.9-
54.4 ug/m3 with outdoors collections ranging from 18.4-146.1 ug/m3. Graphic presentation of the
daily indoor/outdoor variation is presented in Figure 32. Indoor RSP concentrations (ug/m3)
were found to correlate with the outdoor air mass concentration ( R=0.8861) during the
collection period.
Concentrations of B(a)P and total carcinogenic PAH observed in outdoor samples
collected at KHS-Ostrava were observed to be in good agreement with the three primary
stationary monitoring site samples analyzed by the Czech firm ECOCHEM. B(a)P
concentrations from the continuous outdoor monitoring platforms are listed in Table 8 for
comparison purposes. Outdoor concentrations of B(a)P ranged from 1.3-20.2 ng/m3 at KHS-
Ostrava.
Graphic representation of B(a)P and total carcinogenic PAH from the indoor and outdoor
samples collected at KHS-Ostrava is depicted in Figure 33. Indoor B(a)P concentrations were
found to be in general agreement with those observed for daytime PEM measurements. Indoor-
16
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Outdoor B(a)P concentrations were determined to have a correlation of R=0.9254. The use of
open windows to affect human comfort, as well as the fact that there were no reported PAH
emission sources within the facility, certainly influenced the degree to which outdoor and indoor
B(a)P levels were correlated.
Indoor/Outdoor PM2 s XRF Analysis
Data from elemental analysis performed upon indoor and outdoor samples collected at
KHS-Ostrava is presented in Table 9-10. Appreciable concentrations of sulfur, silicon, chlorine,
potassium, magnesium, iron, copper, zinc, bromine, barium, and lead were detected by the XRF
procedures. These concentrations in some respects are not dissimilar to those reported for other
areas of the Czech Republic noted as having high particulate levels (Czech Hydrometerological
Institute, 1992). It is notable that suspect carcinogenic elements (chromium, nickel and arsenic)
are present in concentrations exceeding those usually found in urban areas of major US cities.
While source apportionment is currently not present on this data set, it is reasonable to conclude
that the concentration of S,V, Zn, As, and Se species among other elements, reflect the impact
of industrial emission sources (e.g.., coke ovens, steel manufacturing). Residential heating
emissions (oil+coal furnaces) may also influence ambient metal concentrations in Ostrava.
Indoor-outdoor fine particle mass was determined to correlate (R2=0.8861). This data is
presented in Table 11. Similar comparisons revealed that ambient indoor and outdoor
concentrations of S, K, Ti ,Fe, Cu, Br, and Pb correlated (R2 generally exceeding 0.6) between
paired species. Calculation of elemental indoor/outdoor mass ratios and enrichment factors was
performed as detailed in Table 12. Enrichment is the process where the indoor mass fraction of a
given specie deviates from the ambient mass fraction due to a lack of equilibration or clearance at
the measurement point. Chlorinated species collected indoors were determined to be depleted
with respect to those outdoors (0.5 ratio). Enrichment factors for species representing crustal
matter (Si, K, Ca, Ti, and Fe) exceed 1.0, and may be indicative of track-in by KHS-Ostrava
entrees.
The ratio of ambient B(a)P to Pb concentration is a useful determinant of PAH emission
sources. This ratio is typically around 0.01 when mobile sources are the dominant PAH source in
ambient air. Values exceeding 0.03 and higher will generally indicate that other sources, such as
coke oven emissions, have a greater influence upon the urban air shed. As can be seen in Figure
34, B(a)P/Pb ratios indicate that starting around October 29th, industrial sources probably
contributed significantly to the fine particulate matter (ratios >0.03). Fluctuations in the ratios
give an excellent indication of changing weather patterns (wind, precipitation). This short 14 day
study provides evidence that mobile source emissions rarely were the source of the majority of
the fine particulate matter in Ostrava during the time period under surveillance. Coke ovens,
along with other major industrial point sources and possibly residential coal heating in the Ostrava
area are presumed to be the origin of much of the fine particulate matter detected in this study
based upon elemental analysis of ambient air particulate. Residential heating using various coal
mixtures has been espoused to be a significant contributor to ambient air pollution in the Ostrava
17
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area (J. Novak and Tom Hartlage, personal communipation). Temperatures were transitional
during the time of the study and residential heating probably was a minor contributor to overall
ambient PM^s mass and PAH levels. Source apportionment analysis upon the data presented
from indoor/outdoor monitoring at the KHS-Ostrava site will need to be conducted to more fully
estimate local and point source contribution to ambient particulate concentrations.
18
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References i
Binkova, B., J. Lewtas, I. Miskova, J. Lenicek and R. Sram, "DNA adducts and personal air
monitoring of carcinogenic polycyclic aromatic hydrocarbons in an environmentally exposed
population", Carcinogenesis, 16, 1037-1046 (1995).
CHMI, "Air pollution in the Czech Republic in 1992", Czech Hydrometeorological Institute, Air
Quality Protection Department, Prague (1994).
Lewtas, J., D. Walsh, R. Williams and L. Dobias, "Air pollution exposure-DNA adduct dosimetry
in humans and rodents: Evidence for nonlinearity at high doses", Mutation Research (in press).
Vit, M., C. Kantor, I. Tomasek and J. Volf, "Report No. 5-Silesia Environmental Health
Report", (1995).
Watts, R., J. Lewtas, R. Stevens, T. Hartlage, J. Pinto, J. Miskova, I. Benes, F. Kotesovec, K.
Hattaway and R. Williams, "Czech-US EPA Health Study: Assessment of personal and ambient
air exposures to PAH and organic mutagens in the Teplice district of Northern Bohemia", Int. J.
Environ. Anal Chem., 56:271-287 (1994).
Williams, R., L. Brooks, R. Stevens, V. Marple and J. Lewtas, "Field test and laboratory
evaluation of a lightweight, modular designed, personal sampler for human biomarker studies",
AWMA Symposium on Toxic and Related Air Pollutants, EPA/600/R-92/131, pp. 998-1003
(1992).
Williams, R., J. Meares, L Brooks, R. Watts and P. Lemieux, "Priority pollutant PAH analysis of
incinerator emission particles using HPLC and optimized fluorescence detection", Int. J. Environ.
Anal. Chem., 54:299-314 (1994).
Willis, R., Ellenson, W., Pinto, J., Hartlage, T., Novak, J., Dosdalek, H., L. Cernikovsky and V.
Bures, draft report entitled "Ostrava Air Quality Monitoring and Receptor Modeling Study", US
EPA, RTF, NC. (January 1997).
19
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48
-------
ACTIVITY
Issue daytime
PEM1
Collect 1 st urine
Collect daytime
PEM and issue
nighttime PEM
Recover
nighttime PEM
Recover 2nd
urine
Administer
survey
instrument
Collect blood
specimen
Process PEM
samples
Process
biological
samples
Table I. Ostrava Health Study Testing Regimen
Monday
8:00 am
Group 1-
Day 1
X2
X
Monday
4:00 pm
Group 1-
Day 1
X
X
Tuesday
8:00 am
Group 1-
Day2
X
X
X
X
X
X
Thursday
8:00 am
Group 2--
Day 1
X
X
Thursday
4:00 pm
Group 2--
Day 1
X
X
Friday
8:00 am
Group 2--
Day 2
X
X
X
X
X
X
: Personal exposure monitor.
2X's indicate the planned collection of environmental and biomarker samples from each
study participant as defined by grouping.
49
-------
Table 2. HPLC Detection Parameters and Quantitation Limits
PAH*
Pyrene
B enza(a)anthracene
Chrysene
B enz(b)fluoranthene
B enz(k)fluoranthene
Benzo(a)pyrene
diB enz(ah)anthracene
B enz(ghi)perylene
Indeno(cd)pyrene
Excitation (nm)
276
265
265
290
290
290
298
302
302
Emission (nm)
391
380
380
430
430
430
440
500
500
ILOD**fpe/fin
1.4
3.6
0.3
7.6
0.3
0.5
5.8
32.9
0.4
OL***fn2/m3^
0.5
1.2
0.1
2.6
0.1
0.2
2.0
11.4
0.2
*Listed PAHs are IARC registered animal carcinogens with the exception of pyrene.
* "Instrument Limit fif E>etectioa, based upon a 10 jil standard injection.
***£)uantifiable Limit based upon ILOD as well as air volume collected, values represent a
16 hour collection at 1.5 1/min.
50
-------
Table 3. Inventory of Environmental and Biological Specimens
ID Number/Period
I/ Day
1 /Night
2/Day
2 /Night
3/Day
3 /Night
4/Day
4 /Night
5/Day
5 /Night
6/Day
6 /Night
7/Day
7 /Night
8/Day
8 /Night
9/Day
9 /Night
10/Day
10 /Night
11/Day
11 /Night
12/Day
12 /Night
13/Day
13 /Night
14/Day
14 /Night
15/Day
15 /Night
16/Day
16 /Night
Male
Female
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
. X
X
X
X
X
X
X
X
Weekl
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U.PEM.S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
UPEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
Week 2
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
UPEM
U,PEM,B,S
U,PEM
U.PEM.B.S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S .
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
Week 3
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
Week 4
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S -
U,PEM
U.PEM.S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
1-30 represent volunteer 3D numbers, Day-Night represents when PEM exposure started. X=Gender,
U=Urine collection, PEM=Personal Exposure Monitoring, B=Blood collection, S=Survey collected.'
51
-------
Table 3. Inventory of Environmental and Biological Specimens (continued)
ID Number/Period
17/Day
17 /Night
18/Day
18 /Night
19/Day
19 /Night
20/Day
20 /Night
21/Day
21 /Night
221 Day
22 /Night
23/Day
23 /Niglit
24/Day
24 /Night
2S/Day
25 /Night
26/Day
27 /Night
27/Day
27 /Night
28/Day
28 /Night
29/Day
29 /Night
30/Day
30 /Night
Male
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Female
X
X
X
X
Weekl
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
Week 2
U.PEM
U,PEM,B,S
U,PEM
U.PEM.B.S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
Week 3
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.P-EM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM ,
U,PEM,B,S
U.PEM
U,PEM,B,S
Week 4
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U.PEM
U,PEM,B,S
U,PEM
U,PEM,B,S
1-30 represent volunteer ED numbers, Day-Night represents when PEM exposure started. X-Gender,
U=Urine collection, PEM=Personal Exposure Monitoring, B=Blood collection, S=Survey collected.
52
-------
Study
Week
Weekl
Week 2
Weeks
Week 4
4 Week
Average
Table 4. Summary of Personal Exposure Monitoring
PM2 5 Particle Concentrations (ug/m3)
Day
Range
30.5-404.0
31.0-277.8
29.5-474.6
14.5-87.7
Average
RSP ± S.D.
107.0 ±95.7
92.8 ±65.6
126.7 ±92.1
34.9 ±17.5
90.3 ±39.5
Night
Range
12.0-281.8
10.5-83.0
16,4-107.4
5.09-80.1
Average
RSP ± S.D.
47.4 ±52.83
44.2 ±22.0
58.9 ±27.5
22.3 ± 17.8
43 .2 ±15.3
Average Total
24 Hour
Exposure ± S.D.
64.7 + 60.5
58.9 ±30.7
77.8 ±36.1
27.6 ±18.7
57.3 ±21.3
Values represent summation of all 30 participants each week. S.D.=Standard deviation in jig/m3.
53
-------
Table 5. Summary of Personal Exposure Monitoring
B(a)P Concentrations (ng/m3)
Study
Week
Weekl
Week 2
Weeks
Week 4
4 Week
Average
Day
Range
0.7-22.0
1.6-13.2
1.2-13.3
1.1-6.3
Average
B(a)P ± S.D.
7.4 ±7.2
3.6 _± 3.2
4.9 ±2.9
3.0 ±1.6
4.7 ±1.9
Night
Range
0.4-4.1
0.7-22.0
1.0-14.0
0.3-8.5
Average
B(a)P ± S.D.
1.1 ±1.1
6.5 ±5.8
4.1 ±2.6
2.2 ±1.6
3.5 ±2.3
Average Total
24 Hour
Exposure ± S.D.
2.6 ±2.2
6.0 ±4.7
4.4 ±2.4
2.5 ±1.6
3.9 ±1.7
Values represent summation of all 30 participants each week. S.D.=Standard deviation in ng/m3.
54
-------
Table 6. Summary of Personal Exposure Monitoring
24 Hour Total Carcinogenic PAH Exposure (ng/m3)
Study
Week
Weekl
Week 2
Week3
Week 4
4 Week
Average
Day
Range
0.5-224.9
0.4-393.2
13.5-77.6
1.5-47.6
Average
Carcinogenic
PAH's ±S.D.
68.6 ±71.4
28.6 ± 72.7
30.5 ±17.8
18.8 ±12.5
36.6 ±21. 9
Night
Range
0.5-27.9
1.1-226.6
5.3-71.7
3.6-56.3
Average
Carcinogenic
PAH's±S.D.
9.9 ± 7.4
46.7 ±49.6
31.0+18.6
15.6±11.8
25.8 ±16.5
Average Total
24 Hour
Exposure ± S.D.
22.8 ± 20.9
44.7 ±41.6
31.2+16.4
17.4+17.4
29.0 ±11.9
Values represent summation of all 30 participants each week. S.D.=Standard deviation in ng/m3.
55
-------
Table 7. Indoor and Outdoor Ostrava Sample Collection Data
* "" % ' ^/'•w
Start Filter No- Particle mass (rag) " tu3 Collected iWGn. C
Bate Inside Outside Inside Outside Inside Outside Inside
10/27/95
10/28/95
10/29/95
10/30/95
10/31/95
11/01/95
11/02/95
1 1/03/95
11/04/95
11/05/95
11/06/95
11/07/95
11/08/95
11/09/95
TM615
TM612
TM579
TM578
TM555
TM556
TM540
TM666
TM665
TM663
TM661
TM561
TM560
TM558
TM614
TM613
TM577
TM576
TM554
TM539
TM542
TM667
TM664
TM662
TM659
TM660
TM559
0.67
0.41
0.64
0.78
0.38
0.25
0.18
0.15
0.17
0.13
0.23
0.17
0.22
0.23
1.42
1.35
1.79
1.26
0.80
0.45
0.32
0.26
0.40
0.51
0.43
15.0
13.2
14.1
14.4
14.5
14.3
14.3
14.7
14.4
14.5
14.1
14.2
14.2
14.5
14.4
15.0
12.2
14.4
13.8
14.4
13.5
14.1
13.8
13.9
14.9
1500
1411
1418
1429
1449
1430
1431
1424
1443
1441
1437
1420
1456
1436
-«\ >
ollected Particle (ug/ra3)
Outside-
1500
1426
1400
1440
1435
1440
1417
1444
1425
1413
1452
-Inside
45.0
31.2
45.4
54.4
26.4
17.2
12.8
10.3
12.0
8.9
16.0
12.2
15.4
15.7
Outside
98.7
90.0
146.1
87.6
58.4
31.3
23.7
18.4
29.3
37.1
28.6
Particle
Concentration
fa/Out <%)
45.6
34.7
31.1
62.1
45.3
55.2
54.0
55.8
40.9
43.2
42.8
56
-------
Date
October 27
October 28
October 29
October 30
October 31
November 1
November 2
November 3
November 4
November 6
November 7
Table 8. Outdoor B(a)P Concentrations (ng/m3)
KHS-Ostrava
1.3
3.8
20.16
8.73
13.76
3,84
4.3
1.33
9.82
6.43
10.45
Zabreh
5.4
1.8
3.3
0.9
4.0
2.4
3.5
Radvanice
3.4
5.7
15
11
Privoz
3.0
8.5
13.2
11.2
9.1
4.2
5.1
2.0
3.0
3.8
3.7
Values from Zabreh, Radvanice, and Privoz were determined during the continuous 30 day
monitoring study running concurrent with the Ostrava Health Study. These values were provided
by the Czech firm ECOCHEM.
57
-------
Table 9. Indoor Fine Particle Concentrations (ng/m3)
?inc
Mass
AL
SI
P
s
CL
K
CA
TI
V
CR
MN
FE
NI
CD
ZN
AS
SB
BR
RB
SR
I
BA
PB
10/27
44978
1S1.9
230.0
3618.0
239.7
686.2
193.1
18.9
8.4
3.0
24.1
526.1
11.4
316.8
8.6
13.1
68.9
10/28
31243
106.2
2606.0
188.3
568.7
71
13.9
216.8
109.2
8.4
9.9
2.6
3.4
38.9
50.9
10/29
45432
172.1
48.7
3453.5
259.2
604.0
177.9
23.3
5.6
2.5
11.5
247.6
10.0
178.3
14.2
4.1
22.7
31.6
96.3
10/30
54414
157.2
319.3
5121.4
337.7
676.2
229.4
18.5
8.0
9.8
255.5
8.8
408.2
9.9
2.1
18.1
2.4
38.7
100.7
10/31
26432
173.3
247.6
2850.6
235.0
267.6
316.0
16.0
11.8 .
194.5
4.0
151.7
7.4
7.5
4.0
48.1
11/1
17243
163.0
193.9
1306.9
380.7
164.5
226.2
13.0
2.4
8.9
164.9
3.4
339.4
35.4
11/2
12788
191.8
39.6
775.7
187.7
100.9
162.2
5.9
142.3
4.3
147.7
4.3
33.5
11/3
10258.0
110.5
124.5
30.6
661.6
313.5
119.0
216.0
12.8
2.1
18.7.
258.9
248.0
3.9
28.9
11/4
11989.0
128.9
143.9
1052.4
129.0
142.2
171.1
2.2
61.3
38.6
3.2
1.9
33.4
29.6
11/5
8867.0
160.8
41.5
920.8
90.7
84.9
45.9
21.1
5.5
4.8
64.3
65.0
2.4
29.3
18.3
11/6
16048.0
196.6
1329.0
250.4
136.0
208.8
5.5
110.0
5.8
133.2
6.8
31.2
50.1
11/7
12226.0
118.0
90.6
53.6
999.5
205.0
93.6
136.6
45.5
40.5
6.0
30.2
25.7
11/8
15427.0
155.8
200.4
1023.4
226.8
167.5
227.5
86.6
17.2
66.2
10.2
1.7
6.5
2.4
43.1
11/9
15676.0
246.0
838.2
271.6
177.4
238.5
14.3
377.6
3.6
7.7
164.9
15.4
1.9
5.0
2.2
42.1
Values determined by XRF analysis of PMW collected ambient air particulate at KHS-Ostrava. Sampler located in an
unused office area. Values have been blank corrected. Only data greater than 2 X sigma(analytical uncertainty) is
presented.
58
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Table 10. Outdoor Fine Particle Concentration (ng/m3)
Fine
Mass
AL
SI
S
CL
K
CA
TI
V
CR
MN
FE
NI
CU
ZN
AS
SE
BR
RB
SR
I
BA
PB
10/27
98724,0
204.3
406.4
6416.3
834.3
1361.3
261.9
28.1
14.6
5.1
60.1
1248.6
4.3
15.8
560.8
22.9
3.2
22.1
4.5
26.8
123.2
10/28
90029.0
239.2
4785.9
1192.9
1043.3
153.6
29.6
2.9
21.4
480.8
8.8
11.4
233.5
12.9
3.0
23.2
3.7
17.0
47.5
107.6
10/29
146148.0
511.0
790.9
7168.3
5336.4
1296.0
219.4
38.6
3.5
29.9
936.6
25.9
437.4
14.1
50.1
7.7
4.2
35.5
133.6
205.6
10/30
87639
234.8
5341.5
1962.2
675.1
87.6
19.1
8.0
3.9
11.4
334.5
12.7
633.7
15.1
3.2
27.1
25.8
130.7
10/31
58413.0
188.6
4572.4
1780.5
456.2
145.2
17.7
6.3
5.0
43.2
492.2
10.5
430.5
6.5
23.6
105.4
11/1
31250.0
163.9
2075.6
1020.8
194.4
64.7
14.5
5.3
10.8
215.9
10.5
579.8
8.6
1.7
7.4
2.3
48.5
11/2
23697.0
101.3
1544.1
840.1
171.5
114.7
15.0
2.3
26.7
412.8
7.6
531.8
9.3
2.0
9.1
3.3
64.8
11/3
18396.0
119.0
1146.4
502.8
129.9
65.2
4.7
3.8
30.0
321.4
3.5
11.8
350.5
4.5
2.6
56.2
11/4
29341.0
140.4
55.6
2389.3
1395.4
222.8
41.0
44.0
74.2
1.7
12.6
1.8
3.2
41.1
73.6
11/6
37109.0
66.4
2453.6
1711.6
168.4
38.3
7.8
171.9
8.7
284.3
13.8
22.5
42.8
79.6
11/7
28556.0
46.7
2017.7
1453.1
139.3
65.3
2.3
50.4
3.2
74.2
11.4
2.3
56.2
Values determined by XRF analysis of PM^ collected ambient air particulate at KHS-Ostrava. Sampler located on an
outdoor monitoring platform already operating. Values have been blank corrected. Only data greater than 2 X
sigma(analytical uncertainty) is presented.
59
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60
-------
Table 12. KHS-Ostrava Indoor/Outdoor Correlations,
Ratios, and Enrichment Factors
Mass
Si
S
Cl
K
Ca
Ti
Mn
Fe
Cu
Zn
Br
Pb
Correlation
0.886
0.177
0.882
0.032
0.922
-0.069
0.929
0.810
0.878
0.720
0.867
0.735
0.886
I/O Ratio
0.56
1.41
0.58
0.22
0.69
2.43
0.81
0.59
0.65
0.53
0.50
0.47
0.54
Enrichment Factor
3.0
1.2
0.5
1.5
5.2
1.7
1.3
1.4
1.2
1.1
1.0
1.2
For a given elemental species, the enrichment factor is calculated as the ratio of the
indoor mass fraction to the outdoor mass fraction where the mass fraction is the
mass concentration of the species divided by the PM2 5 mass concentration.
61
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