United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
P.O. Box 15027
Las Vegas NV 89114
EPA-600/4-79-072
November 1979
Research and Development
&EPA
Great Smoky Mountain
Preliminary Study for
Biosphere Reserve
Pollutant Monitoring
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad categories
were established to facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously planned to foster
technology transfer and a maximum interface in related fields. The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL MONITORING series/This series
describes research conducted to develop new or improved methods and instrumentation
for the identification and quantification of environmental pollutants at the lowest
conceivably significant concentrations. It also includes studies to determine the ambient
concentrations of pollutants in the environment and/or the variance of pollutants as a
function of time or meteorological factors.
This document is available to the public through the National Technical Information
Service, Springfield. Virginia 22161
-------
EPA-600/4-79-072
November 1979
GREAT SMOKY MOUNTAINS PRELIMINARY STUDY FOR
BIOSPHERE RESERVE POLLUTANT MONITORING
by
G. B. Wiersma and K. W. Brown
Exposure Assessment Research Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89114
R. Herrmann
National Park Service
Atlanta, Georgia 30349
C. Taylor and J. Pope
Environmental Research Laboratory
Athens, Georgia 30605
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
, OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89114
-------
DISCLAIMER
This report has been reviewed by the Environmental Monitoring Systems
Laboratory-Las Vegas, U.S. Environmental Protection Agency, and approved for
publication. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
-------
FOREWORD
Protection of the environment requires effective regulatory actions based
on sound technical and scientific information. This information must include
the quantitative description and linking of pollutant sources, transport
mechanisms, interactions, and resulting effects on man and his environment.
Because of the complexities involved, assessment of exposure to specific
pollutants in the environment requires a total systems approach that
transcends the media of air, water, and land. The Environmental Monitoring
Systems Laboratory-Las Vegas contributes to the formation and enhancement of
a sound monitoring data base for exposure assessment through programs
designed to:
•develop and optimize systems and strategies for
monitoring pollutants and their impact on the
envi ronment
• demonstrate new monitoring systems and technologies
by applying them to fulfill special monitoring needs
of the Agency's operating programs
This report presents the results of the field sampling program carried
out in the fall of 1977. This was a multi-media, integrated sampling effort.
Data collected gave estimates of detection limits, variability and levels of
certain pollutants. Problems of logistics and access were dealt with. This
study provides a basis for an expanded sampling program in the Great Smoky
Mountain Biosphere Reserve which will help achieve the ultimate goal to
develop a responsive and cost effective pollutant monitoring system for
biosphere reserves in general.
George B. Morgan
Director
Environmental Monitoring Systems Laboratory
Las Vegas
iii
-------
SUMMARY
A preliminary sampling program was initiated in the Great Smoky Mountains
National Park, Tennessee, and North Carolina. This national park of 209,000
hectares was selected to be a part of the Southern Appalachian Biosphere
Reserve cluster. It serves as a permanent reservoir of genetic material and
a site where natural ecosystems can be sampled, studied, and preserved.
An interest in the state of the environment as indicated in the framework
of the Man and Biosphere Program (MAB) necessitates the assaying and
documentating of the environmental quality in these preserves. For this
reason, a monitoring program was initiated. This initial program, a mutual
effort by the U.S. Environmental Protection Agency and the U.S. National Park
Service, had two objectives. The first objective was to determine the levels
of trace elements and organic contaminants in physical and biological media.
The second objective, following data analysis and evaluation, was to design
an effective and cost-efficient pollutant monitoring system.
Physical and biological media sampled included air, water, soils, litter,
and various plant species. Analytical results of these samples showed a
variety of elemental contamination. The concentration of lead in litter at
four sampling sites was of particular importance. The concentration ranged
from 246 to 469 parts per million. These data, similar to those reported by
other researchers, showed that lead levels increase with altitude.
A field sampling error of plus or minus 10 percent at the 95 percent
confidence level was desired. The number of samples required to satisfy this
condition for a permanent monitoring system, based upon the sample/element
combination, was determined and used in subsequent studies.
Environmental monitoring, as defined by the U.S. Environmental Protection
Agency, is the systematic collection of physical, chemical, biological, and
related data pertaining to environmental quality, pollution sources, and
other factors that influence or are influenced by environmental quality.
Environmental quality data are essential for determining the exposure of
critical populations at risk. Such data are obtained by establishing
monitoring systems to identify and measure pollutants and their
concentrations in-air, water, vegetation, soil, and food. The identification
and measurement of pollutants in preserved areas, such as the biosphere
reserves, may permit the monitoring of subtle deleterious processes that may
be masked in areas of high impact. In identifying and measuring the exposure
of receptor communities to chemical or physical agents, monitoring data
provide the basis for quantitating the contributions of environmental
pathways for each chemical or physical form of the pollutant.
IV
-------
CONTENTS
Foreword Hi
Summary 1v
Figures vi
Tables vii
Introduction 1
Conclusions 5
Field sampling methods 6
Soil and vegetation sampling and site description 6
Water sampling 9
Air samples 10
Analytical techniques and results ..... 11
Water 11
Air 19
Vegetation and litter 28
Soil analysis 44
References 46
Appendix 49
-------
FIGURES
Number Page
1. Sampling site locations in the Great Smoky Mountains
National Park 7
2. Gas chromatogram (FID) of internal standards, deuterated
anthracene, and 1,2-diphenyl hydrazine 13
3. Gas chromatogram (FID) of biosphere reserve XAD-8
extract 15
4. Gas chromatogram (FID) of biosphere reserve combined
extracts 15
5. Computer-reconstructed gas chromatogram of biosphere
reserve XAD-8 extract 17
6. Toluene (confirmed) 18
7. Chromatogram of petroleum ether extract of sample 3C-3 ... 26
8. Chromatogram of petroleum ether extract of sample 1C-4 ... 27
VI
-------
TABLES
Number
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Summary of Types and Numbers of Samples Collected at
Summary of Analyses of Elements Determined by ICPES
and SSMS
Summary of Analyses of Elements Determined by SSMS Only. . . .
Results of Multielement Analyses using ICPES and SSMS
Summary of Retention Volumes (cc) for 63Ni Gas Chromatographic
Analyses of Charcoal Filter Samples Mo. 1C-4 and 3C-3. . . .
Summary of Trace Element Values in Forest Litter from
Site 11
Summary of Trace Element Values in Mettle Leaves from
Site 11
Summary of Trace Element Values in Rhododendron Leaves
from Site 11
Summary of Trace Element Values in Forest Litter
from Site 12
Summary of Trace Element Values in Rhododendron Leaves
from Site 12
Summary of Trace Element Values in Christmas Fern
from Site 12
Summary of Trace Element Values in Forest Litter
from Site 13
Summary of Trace Element Values in Forest Litter
from Site 13
Summary of Trace Element Values in Witch Hobble
from Site 13
Page
8
20
21
22
24
29
30
31
32
33
34
35
36
37
vn
-------
TABLES (Continued)
Number Page
15. Summary of Trace Element Values in Forest Litter
from Site 14 38
16. Summary of Trace Element Values in Rhododendron Leaves
from Site 14 39
17. Summary of Trace Element Values in Yellow Birch
from Site 14 40
18. Coefficients of Variation for Elemental Levels in Vegetation
Samples Collected in the Great Smoky Mountains Biosphere
Reserve 41
19. Results of Soil Analyses for Great Smoky Mountains 43
viii
-------
INTRODUCTION
Man's impact on the environment is far-reaching and at times
catastrophic. Gone are the days when the pollution emitted by man was
assumed to impact only his immediate surroundings. Today, pollution problems
are recognized as truly global in nature; they transcend geographic and
political boundaries.
Elgmork et al. (1973) reported that snow in Norway contained several
pollutants. They found levels of lead in the snow up to 98 micrograms per
liter (yg/1), sulphur levels of 8.5 milligrams per liter (mg/1), and pH
values as low as 3.25. The remoteness of these sampling areas from Norway's
limited automobile and industrial areas precluded pollutant deposition from
local sources. The researchers concluded that these pollutant levels
resulted from contaminated afr masses being brought in by low-pressure
systems from the great industrial and urban areas of western and central
Europe. Another study by Johnson et al. (1972) showed that streams in New
England were acidified primarily through the washout of sulphur compounds
during local rains. Most of this sulphur originated from the combustion of
fossil fuels from large industrial centers of the eastern and central United
States. Schlesinger et al. (1974) also reported that lead, cadmium, and
mercury were present in precipitation on Mount Moosilauke in New Hampshire.
They determined that low pressure-system tracks in North America coming from
the large population and industrial areas of the central and mid-Atlantic
regions of the United States converged on the northern New England States.
Lazarus et al. (1970) reported that increased levels of lead, zinc,
copper, iron, nickel, and manganese were found in rainwater collected by a
nationwide precipitation network. They concluded that man's industrial
activities were the primary source of these pollutants in the rainwater. The
highest overall concentrations occurred in the northeastern portion of the
United States. Also, a significant statistical correlation existed between
the lead concentrations at each precipitation sampling station and the
quantity of gasoline sold in the vicinity of each of the collection points.
Chow and Earl (1970), studying lead aerosols in the vicinity of San
Diego, California, reported that only a small fraction of the lead aerosols
are deposited near the source of emission. They hypothesized that the
majority of lead particulates are transported by major air currents and
deposited throughout the world. Hirao and Patterson (1974) studied lead
levels in Thompson Canyon, a remote site on the High Sierra Crest. According
to their data, the 14-square-kilometer (km ) watershed received 16 kilograms
-------
(kg) of deposited lead per year. It was further determined that 97 percent
of this lead was from anthropogenic sources. They stated:
"These findings show that a widespread assumption, that lead
pollution is mainly confined to urban complexes and is
essentially absent in open country, is improbable. ..."
In addition to lead, other elements have been shown to be transported on
a global basis. Weiss et al . (1971) sampled the Greenland icecap and
presented data showing mercury levels that indicated a possible buildup of
mercury in the ice sheet. For example, in samples representing deposition
prior to 1952, the mean mercury concentration was 60 ± 17 nanograms per
kilogram (ng/kg) of water. Samples representing deposition from 1952 to 1965
had a mean concentration of 125 ± 52 ng/kg of water.
Zoller et al. (1974) analyzed atmospheric particulate material at the
South Pole for 22 elements. Antimony, lead, selenium, and bromine were all
highly enriched over what could be expected from earth crustal values. They
postulated that the source of these compounds was from high-temperature
combustion of volcanic activity or from manmade fossil-fuel burning.
Global transport has also been confirmed for other pollutants such as
DDT. For example, Anas and Wilson (1970) reported that northern fur seals
collected on the Pribilof Islands, Alaska, in 1969 contained DDT and its
isomers in both the nursing pup's fat tissue and in the mother's milk.
Concern over the widespread global contamination from man's activities
has been one of the driving forces behind the attempt to establish a global
network of biosphere reserve sites. The Study of Critical Environmental
Problems Report (Massachusetts Institute of Technology, 1970) stated:
"Over the past few years, the concept of the earth as a
'spaceship1 has provided many people with an awareness of
the finite resources and the complex natural relationships
on which man depends for his survival. These realizations
have been accompanied by concerns about the impacts that man's
activities are having on the global environment. Some concerned
individuals, including well-known scientists have warned of both
imminent and potential global environmental catastrophes."
A variety of organizations and committees—including the International
Task Force of the Global Network for Environmental Monitoring; the Global
Monitoring Task Force of SCOPE (Scientific Committee on Problems of the
Environment); the Man and Biosphere Expert Panel on Pollution; the Study of
Critical Environmental Problems (SCEP); Task Force II, Committee on
International Environmental Affairs; and the SCOPE Commission on
Environmental Monitoring Assessment—have called for the formation of a
global monitoring network.
The United Nations Conference on the Human Environment (Man and
Biosphere, 1974) held in Stockholm in June 1972 recommended the establishment
-------
of the United Nations Environment Program. It also recommended the
establishment of EARTHWATCH, which has a four-pronged program including
monitoring, research, evaluation, and information exchange. The ultimate
objective of EARTHWATCH was the establishment of a Global Environmental
Monitoring System (GEMS). As part of this Global Environmental Monitoring
System, it was recommended that biosphere reserves -be established. The UN
Conference on the Human Environment in 1972 also recomemnded that biological
reserves be established within the framework of the Man and Biosphere
Program. In addition, a report entitled "Man's Impact on the Global
Environment," published by the Massachusetts Institute of Technology in 1970,
recommended similar entities, calling them ecological baseline stations in
remote areas or biosphere reserves.
Biosphere reserves may be defined as undisturbed and protected natural
background areas of the Earth where life processes occur with minimal human
interference. The requirements for, and the value of, biosphere reserves
have previously been described in the report of the Ad Hoc Task Force on GNEM
(Global Network for Environmental Monitoring) (1970) and the SCOPE Report No.
3 (Munn, 1973).
Specifically, the biosphere reserves were established to:
1. provide a permanent record of the state of the environment;
2. ensure the availability of undisturbed areas from which background
data on pollutant levels could be obtained;
3. give indication of increasing levels of global pollution; and
4. serve as repositories for natural sources of genetic pools of animal
and plant species.
Franklin (1976, 1977) identified the research and monitoring activities
for which the reserves could be used. These included:
1. long-term baseline studies of environmental and biologic features;
2. research to help develop management policies for the reserves;
3. experimental or manipulative research;
4. environmental monitoring; and
5. study sites for selected MAB research projects.
A detailed concept paper has been published on the general approach to a
pollutant monitoring system for biosphere reserves (Wiersma et al., 1978).
In addition results from preliminary studies on the Great Smoky Mountains
were presented at the Fourth Joint Conference on Sensing of Environmental
Pollutants (Wiersma et al., 1977).
-------
This report is the compilation and analysis of data generated from a
monitoring study conducted in the Great Smoky Mountains National Park in
cooperation with the U.S. Environmental Protection Agency (EPA.) and the U.S.
National Park Service. The objectives were to determine minimum pollutant
levels, to identify the variability of collected samples, and to evaluate
sampling techniques. Media sampled included air, water, unincorporated
litter, soils, and vegetation.
-------
CONCLUSIONS
The results and techniques identified indicate that sampling problems
such as logistics and access into relatively remote areas are not limiting
factors in the establishment of a pollutant monitoring system. Analytical
detection limits employing techniques as described in this report for
vegetation, soils, and litter were adequate for the completion of the stated
objectives. Detection limits for selected trace elements in air will have to
be improved either by analytical techniques or in sampling equipment design.
Field sampling error, which was relatively high, can be adjusted by sampling
design.
The collection of physical and biological data from natural areas within
the Great Smoky Mountains National Park will establish the necessary criteria
to develop a comprehensive pollutant monitoring program. Sampling techniques
used, combined with long-term monitoring data, will serve to identify
baseline conditions, identify pollutant concentrations, determine trends, and
define physical and biological responses to man-induced contaminants.
-------
FIELD SAMPLING METHODS
SOIL AND VEGETATION SAMPLING AND SITE DESCRIPTION
Four sampling sites within the national park were chosen for
investigation. Vegetation, water, and unincorporated litter, defined as
organic debris and its underlying fermentation layer, were collected at each
site. Two of the sites were located on the north slope of the Great Smoky
Mountains, a third on top of a ridge, and the fourth on the south-facing side
of the park. The site locations are shown on Figure 1, labeled as 11, 12,
13, and 14.
Site 11 was located on the north side of the park at an elevation of
about 1,100 m; this site v/as in a mature hardwood/hemlock forest. Species
common in the overstory included hemlock, sugar maple, black cherry, tulip
poplar, and magnolia. The understory was made up primarily of rhododendron.
Nine sampling points were originally planned per site using a 3 x 3 grid
system. The distance between each grid point was to be 200 m. However, the
thick understory and steep slopes at site 11 prevented this sampling scheme.
The nine sampling points were laid out along a trail at 200-m intervals.
Each sampling point was 40 m up slope from the trail .
Unincorporated litter was sampled at 10 locations evenly spaced around a
10-m diameter circle at each of the 9 sampling points at site 11. A 1-liter
sample was collected at each location around the circle. The ten 1-liter
samples were placed in a clean plastic bag and thoroughly mixed. After
mixing, a 0.5-liter aliquot was collected and placed in a polyethylene
container. At each of these 10 locations, a 5-centimeter (cm) deep soil
sample was collected after the unincorporated litter layer was removed. In a
manner similar to the unincorporated litter mixing and sampling techniques,
the 10 soil samples were placed in a clean plastic bag, thoroughly mixed, and
then subsampled. At each of the 10 sample points, 2 species of plants were
sampled. The plant tissues collected were new leaf growth. For site 11, a
1-liter water sample was collected from a tributary stream near Roaring Fork
Creek. Table 1 shows the kinds and number of samples collected at each site.
Sampling site 12 was located on Porters Flat at an elevation of 800 m.
This site was composed primarily of 40-year-old second-growth hardwood.
Hardwoods common in the overstory included hemlock, sugar maple, tulip
poplar, and beech. The method of sampling was identical to that used at sitq
11. A 1-liter water sample was also collected at the footbridge on Porters '
Creek. A summary of the samples collected is presented in Table 1.
-------
v Air Sampling Site
• Soil and Vegetation Sampling Sites
Figure 1. Sampling site locations in the Great Smoky Mountains National Park.
-------
TABLE 1. SUMMARY OF TYPES AND NUMBERS OF SAMPLES COLLECTED AT THE
GREAT SMOKY MOUNTAINS NATIONAL PARK
00
Air Sampling
Sites
Sample Type 123
Air
Trace metals 444
Mercury traps 444
Trace organics 444
Water
Trace metals
Trace organics
Soil
Litter
Vegetation
Rhododendron
Nettl e
Christmas fern
Witch hobble
Wood fern
Yellow birch
Soil, Vegetation, and Water Sampling Sites Total Samples
1 2A 2B 3 4 5 6 7 8 9 10 11 12 13 14 Collected
12
12
12
111111111111111 15
1 11111111 10
9999 36
9999 36
99 9 27
9 9
9 9
9 9
9 9
9 9
-------
Sampling site 13 was located on Mount Collins, about 3.3 km east of
Clingmans Dome at an elevation of 1,800 meters (mj. The topography at this
site was relatively flat. The understory vegetation was dense, composed
primarily of witch hobble, while the overstory was made up of mature red
spruce and Fraser fir. A 3 x 3 grid design with 200 m between sampling
points was used. A 1-liter water sample was collected from a spring 50 m
below the site. Samples collected at this site are shown in Table 1.
Sampling site 14, located on the south side of the park, was 2.5 km north
of the trail head at Smokemount Campground. The elevation at this site was
800 m. Sampling was conducted along Bradley Fork. The techniques used were
identical to those used at sites 11 and 12. The water sample was collected
from a tributary stream of Bradley Fork. The vegetation on this site was
second-growth hardwood, about 40 years old and similar in composition to
vegetation at site 12.
WATER SAMPLING
In addition to the four 1-liter water samples collected at sites 11, 12,
13, and 14, a variety of streams draining both the north and south slopes of
the park were sampled. These sites, chosen with the aid of park personnel,
were representative of the area's main drainage systems.
At each of these sampling sites a 1-liter sample was collected. The
sample was placed in a Teflon bottle and immediately acidified with nitric
acid. In addition, a 19.2-liter glass carboy was filled with water. The
glass carboy had been previously cleaned to remove possible contamination by
trace organics. Each of the 1-liter samples was analyzed for trace
elements. The carboy samples collected for trace organic analyses were
composited with the entire amount extracted.
The water sampling sites identified below are also shown on Figure 1.
1 - Oconaluftee River, at the bridge on Tow String Road
2A - Beechflat Creek, above the road cut on Highway 441 (trace element
sample only)
2B - Beechflat Creek, directly below the road cut on Highway 441
3 - Walker Prong, 30 m east of Highway 441
4 - Twin Creeks, approximately 60 m from the Uplands Field Research
Station
5 - Nolan Creek, about 1.7 km north of Fontana Lake Highway
6 - Beechflat Creek, 1.7 km below the cut on the east side of Highway
441
7 - Abrams Creek, near Cades Cove
8 - Abrams Creek, about 0.4 km east of the Cades Cove area
9 - Little River, about 90 m below the confluence of the Little River
and the Middle Prong of the Little River
10 - Ramsey Cascade Creek, about 2.5 km from the bridge
-------
AIR SAMPLES
Air samples were collected at three sites in the park (see Figure 1).
One site was located at the Uplands Field Research Station near Gatlinburg,
Tennessee (air site 3). A second (air site 2) was located at Clingmans Dome,
the highest point in the park. The third was located at the Wranglers Corral
near the intersection of Tow String Road and the Oconaluftee River on the
south side of the park (air site 1).
At each station, three air samples were collected. One was analyzed for
mercury, the second for trace elements, and the third for trace organics.
The mercury collection system, previously identified by Long et al.
(1973), was composed of a 20-cm long, 5-millimeter (mm) diameter glass tube
filled with silver wool. Air was pumped through the glass tube-silver wool
trap at a flow rate of approximately 50 milliliters per minute (ml/nrin).
After sampling, the trap was sealed, transported to the laboratory, and
analyzed by a direct current plasma emission analytical system.
The second type of air monitoring device, for trace elements, consisted
of a 0.8-micrometer (jim), type AA Mil lipore filter. After collection, the
Millipore membrane filters were analyzed by photon-induced X-ray fluorescence
as described by Jaklevic et al . (1976), Jaklevic et al. (1973), and Dzubay
and Stevens (1975).
The third type of air sampler was a TEMPEST high-volume instrument
utilizing a Bureau of Mines 3B-06 charcoal cartridge and a Whatman prefilter.
Sampling was conducted at a flow rate of 13 cubic meters per hour (m'/h).
The charcoal cartridge and the prefilter were sent to the University of Iowa
and analyzed for organic compounds by standard extraction and gas
chromatograph techniques.
10
-------
ANALYTICAL TECHNIQUES AND RESULTS
WATER
Organic Analyses
Analysis of Purgeable Volatile Organics—
The Environmental Protection Agency's Surveillance and Analysis Division
of Region IV in Athens, Georgia, analyzed this group of samples by the
purge-and-trap method. The results of these analyses using a gas
chromatograph-mass spectrometer (GC-MS) detection system with a minimum
detectable limit of 0.5 mg/liter showed that only methylene chloride,
chloroform, acetone, ji-hexane, and isoctane were found in the samples.
However, the concentrations of these compounds were less than the calibration
blanks: therefore, no purgeable organic compounds will be reported as being
present in the biosphere samples.
Analysis of Non-Purgeable Volatile Organics--
Eight 19.2-liter wide-mouth bottles were washed with detergent and then
rinsed three separate times with tapwater, distilled water, and acetone.
After drying in an oven, each bottle was rinsed with a separate solution of
100 ml of methylene chloride. The washings were combined and then evaporated
to 1 ml with a Kuderna-Danish (K-D) evaporator and micro-K-D. The washings
were analyzed for impurities by gas chromatography using a 6-m x 2-mm i.d.
glass column packed with 1 percent SP-2250 on 100/120 Supelcoport. The
carrier gas used was 27 to 29 ml/min of helium. The injector temperature was
275°C and the FID detector temperature was 300°C. The temperature program
called for 4 min at 50°C, rising 8°C/min to 260°C, with a final hold of 20
min. The injection size was 2 ml, and the attenuation was set so that 40 ng
injected gave 10 to 90 percent deflection. The washings did not show any
contaminants.
After the mouths were sealed with aluminum foil, the sample bottles were
transported to the Great Smoky Mountains. As previously mentioned, the
samples were collected throughout the national park (see Figure 1 for exact
locations). One of the samples was lost during shipment because of container
breakage.
The resins chosen for the accumulator columns were XAD-8, XAD-4/8, and
35/60 mesh Tenax. The XAD-4/8 is an equal dry-weight mixture of XAD-4 and
XAD-8. All had been precleaned and stored for several months under methano1.
About 50 ml of each resin were placed in separate chromatography tubes and
washed with solvent. The XAD resins were washed with acetone and methylene
chloride, and the Tenax was washed with acetone. The last 100-ml portion of
effluent was collected, evaporated, and gas chromatographed as previously
11
-------
described. Solvent impurities were also checked by gas chromatography. If
peaks were present in the chromatograms, the washing process was repeated
until either the chromatograms were free of peaks or the peaks had been
reduced to an insignificant level.
The resins were placed in three separate columns connected in series.
After the sample had passed through, they were stripped of accumulated
organics and examined separately. The first column was XAD-8 because it was
believed to reversibly sorb humic acids. It also served as a protector
column for the XAD-4/8 column, protecting the XAD-4 resin from contamination
by irreversibly sorbed humic material. The third column, Tenax, was used
mainly to accumulate other compounds passing through the two previous
columns.
This sampling train met the requirements of the project but was not
ideal. Water passed from the sample bottle through a 60-mm i.d. Teflon tube
to a glass connector on top of the first column. It went through the column,
out a U-tube, up through the second column, through an inverted U-tube, and
down through the third column. The water was forced through the train by a
peristaltic pump attached to the bottom of the third column. A number of
problems occurred with this system. First, a planned.flow rate of 100 ml/min
could not be maintained. Also, because of the short lengths of resin packing
relative to the entire length of the column, several void areas within the
system occurred. In addition, the columns would not hold the desired 50 ml
of resin.
Because of these problems, the final dimensions and configuration of the
accumulator columns were 14.6 ml of XAD-8 in a 13-cm x 1.2-cm i.d. column
(ratio of length to diameter of 10.8), 26.6 ml of XAD-4/8 in a 13.3-cm x
1.6-cm column (length: diameter 8.3), and 45.5 ml of Tenax in a 14.5-cm x
2.0-cm column (length: diameter 7.2). The flow rate averaged about
40 ml/min.
The analytical techniques were designed to detect organics in water at
0.1 parts per billion (ppb). To test the analytical system, decadeutero
anthracene and 1,2-diphenyl hydrazine were selected as internal standards.
Both of these compounds as well as azobenzene, a degradation product of
1,2-diphenyl hydrazine, are unlikely to be found in water.
Two separate standards were prepared for each of these two compounds in
methylene chloride. One hundred microliters (yl) of each solution was then
dissolved in a liter of water. The liter of standard solution contained
16 yg of the deuterated anthracene and 200 yg of 1,2-diphenyl hydrazine,
which represented approximately 0.1 ppb and 1.0 ppb concentrations,
respectively. The first set was extracted with methylene chloride,
concentrated, and gas chromatographed as described previously for the
sample-bottle washings. The hydrazine (azobenzene) peak was about 60 percent
of full scale while the deuterated anthracene was only about 4 percent of
full scale as shown in Figure 2. The experiment did indicate that a
detection limit of 0.1 ppb would be attainable.
12
-------
CO
q
06
A 1,2 Diphenyl Hydrazine (Azobenzene)
B Deuterated Anthracene
Figure 2. Gas chromatogram (FID) of internal standards, deuterated anthracene, and
1,2-diphenyl hydrazine.
-------
The second liter of standard solution was used to spike the collected
water samples. A 100-ml portion of the standard solution was added to each
of the seven 19.2-liter samples, and a 200-ml portion to the eighth and ninth
sample as they were being extracted. The final concentration of the
anthracene and the 1,2-diphenyl hydrazine standards added to the water
samples was 0.094 yg/1, representing 0.09 ppb and 1.19 ppb, respectively.
The water samples were not refrigerated or preserved in any way, and they
remained sealed with aluminum foil and tape until sampled. A slight deposit
of black sediment was observed on the bottom of each sampled container. This
deposit, however, was not disturbed during the extraction of water from the
bottles.
Sampling was conducted over a 5-day period in 16-hour increments. The
sample train was constantly under a mild vacuum, and traces of air, probably
from the ground-glass joints, could occasionally be seen passing through the
system. After all of the water had passed through the columns, they were
removed from the system. The excess water was drained off, and a stopcock
adapter attached to the bottom of each column. Thirty ml of acetone was then
added to the XAD-8 column, followed by 120 ml of methylene chloride. The
combined collected effluents were mixed in a separatory funnel, with the
small top layer of water separated from the organic layer. The organic
extract was evaporated to 0.5 ml.
The XAD-4/8 column was treated similarly except that 50 ml of acetone and
200 ml of methylene chloride were used. The extract was evaporated to 0.87
ml. A small amount of white precipitate was observed in the extract
following evaporation.
The Tenax column was eluted in two stages. First, 100 ml of acetone was
added. It was dewatered by adding 200 ml of methylene chloride. After
removing the water layer, the organic portion was evaporated to 10 ml. An
additional 250 ml of acetone was added to the Tenax column. After
collecting, it was added to the orignal 10 ml concentrate and evaporated to
1 ml. In addition, solvent blanks were prepared using the same amounts of
solvents plus 10 ml of water.
The samples and the blanks were all examined by GC/FID using the GC
conditions and procedures described previously. Most of the eluted compounds
were found in the XAD-8 (Figure 3). No peaks having different retention
times from those found in the XAD-8 extract were observed in the XAD-4/8 and
Tenax extracts. The XAD-8 extract had nine peaks of 10 percent or more of
full scale. Two of these were the spiked standards. XAD-4/8 had four peaks,
and Tenax had two. The solvent blanks were all acceptable with essentially
no discernible peaks.
After the three individual extracts had been examined by gas
chromatography-mass spectrometry (GC-MS), they were combined and concentrated
to 0.4 ml with a micro-K-D. The gas chromatogram (GC-FID) of this extract
showed only four peaks as large or larger than the deuterated anthracene
standard (Figure 4).
14
-------
A 1,2—Diphenyl Hydrazine
(Azobenzene)
B Deuterated Anthracene
B
Figure 3. Gas chromatogram (FID) of biosphere reserve XAD-8 extract,
A 1,2—Diphenyl Hydrazine
(Azobenzene)
B Deuterated Anthracene
Figure 4. Gas chromatogram (FID) of biosphere reserve combined extracts.
15
-------
The extracts were examined by GC-MS under the following techniques and
conditions. A glass column (3 m x 3 mm) packed with 4 percent SP-2100
(equivalent to SE-30) on 80/100 Supelco was used. The temperature program
was an initial hold at 50°C for 4 minutes, followed by heating to 240°C at
8"C/min. The GC was interfaced to the mass spectrometer by a two-stage glass
frit-type separator. The mass spectrometer was a Varian CH5-DF that operated
at the standard 70 eV and scanned once every 5 seconds. Two-yliter
injections of samples were made. After the source pressure gauge indicated
that most of the methylene chloride solvent had passed through the source,
the filament was turned on and the scans started.
The data were processed on a Varian SS 166 data system equipped with a
dual platter disc and nine-track magnetic tape. The spectra were
computer-matched with a large mass spectral library by the Mass Spectral
Search System at Cyphernetics Corporation in Ann Arbor, Michigan. Personnel
interpretations of the individual spectra were also made.
The XAD-8 extract shown in Figure 5 was the most concentrated and
complex. All contaminants found in the XAD-4/8 and Tenax extracts were also
found in the XAD-8 extract. The two internal standards were only found in
the XAD-8 extract.
The composited extract, similar to the individually examined extracts,
showed peaks in the first and third portions of the chromatograms. The
sensitivity and resolution of the GC-MS system used in this study were less
than the FID gas chromatograph.
The only compound that was definitely identified in the water samples was
toluene (Figure 6). There also was strong evidence for the presence of
dimethyl hexene or methyl heptene, nonane or an isomer, trimethyl benzene or
isomers, ethyl benzene, ethyl toluene, and three phthalate esters. The
computer match also indicated that 2,4-di-t-butyl anisole, 2,5-di-t-amyl
quinone, and 1,2,4-tri-t-butyl anisole may be present; these compounds are
rarely, if ever, found in water.
Only toluene and nonane gave total ion currents stronger than that of the
0.09-ppb deuterated anthracene. It was concluded that no other compounds
were present at greater concentrations than 0.09 ppb. It was believed that
the recoveries of deuterated anthracene and 1,2-diphenyl hydrazine
(azobenzene) from the dosed biosphere reserve sample were 100 percent. The
concentration of nonane was approximately 1 ppb, and the toluene near 2 ppb.
Multielement Analysis
The one-liter water samples that had been preserved with 1 ml of ultrex
nitric acid were analyzed for trace element constituents by two standard
16
-------
SO.OOOi
Ready
20,000-
10.000-
1. Toluene (confirmed)
2. Dimethyl hexene
or methyl heptene
3. Nonane
5. Trimethyl benzene
6. Ethyl toluene
* i IT i i r^ i i " i r T r «r ' i ' i i « i • i
100 110 120 130 140 150 160 170 180 190 200 210 220 230
Spec* 100- 336LM/R.W. XAD-8 WASH 9/28/77 Step Spec #= 1.INT = 1000
30,000-]
20.000-
10.000-
7. Azobenzene*
8. D-io-Anthracene
9. Phthalate
*From 1,2-diphenyl
hydrazine
230 240 250 260 270 280 290 300 310 320 330 340 350 360
Spec # 100- 336LM/ R.W. XAD-8 WASH 9/28/77
Step Spec # = 1,INT = 1000
Figure 5. Computer-reconstructed gas chromatogram of biosphere reserve XAD-8 extract.
-------
100n
Ready
91
92
LjJ
l
57
65
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
Spec 4007 LS 4007LM - 4003LM Step Mass- 1 I/B/S- 10
Figure 6. Computer-reconstructed gas chromatogram confirming
presence of toluene.
18
-------
multielement techniques--!"nductively coupled plasma emission spectrometry
(ICPES), and spark source mass spectrometry (SSMS). The ICPES was used
because it is capable of giving rapid and accurate determinations of a
specific group of 26 elements. The SSMS was used to provide a survey
analysis of the entire spectrum of elements, except for the gases.
The procedures and techniques used for the multielement analysis have been
previously described by Elgmork et al. (1973) and Johnson et al. (1972).
The results, which are summarized in Tables 2 and 3, show the the
concentration range, average concentration, and frequency of occurrence for
each element. Two samples, one from site 2B and the other from site 7, were
not in the data shown in Tables 2 and 3. The reason for their omission was
that the water from site 2B was collected below a construction area and the
water from site 7 was collected at a point just below a cattle-grazing area.
Table 4 summarizes the results of all elements analyzed jointly by ICPES
and SSMS analyses. The limit of detection for the SSMS for all elements was
0.001 mg/liter. The detection limits of ICPES are indicated by less than
values shown on Table 4. The samples for SSMS were prepared in glass
containers and were possibly contaminated with boron and silicon. For this
reason, no analyses for these elements were reported.
As shown on Table 4, these samples all contained very low levels of most
elements. Of the consent-decree elements, only zinc was found.
The zinc in the water sample collected at site 6 is of special interest
because it was collected from an area that occasionally displays a white
deposit on the stream rocks. U.S. National Park Service personnel suspected
this deposit to be an aluminum salt; however, the aluminum concentration,
0.078 pg/liter, is below the average concentration shown on Table 2. This
sample was also higher than the average in manganese content.
AIR
The results from the Millipore filters indicated no detectable levels of
trace elements. Based on the maximum flow rates used and the detection
limits, a "less than" level can be determined. For lead (Pb) it was
estimated that, using a filter with 10.75-cm2 area with a detection limit of
70 ng Pb/cm2 of filter area and a maximum air volume sampled of 14.6 m3, the
minimum detectable limit would be approximately 50 ng of Pb/m3 of air. It is
not unreasonalbe to expect that the air concentration of lead in the park
would be low. Jaklevic et al. (1976) reported that lead levels in air
collected from rural areas contained approximately 100 ng/m3. Chow and Earl
(1970) reported an average lead concentration in air of 50 ng/m3 at Mount
Laguna, 45 miles from San Diego. An increase in flow rate or sampling time
would increase the sensitivity of this system. The air sampling system
employed has, with modification, been used successfully in remote areas of
the Great Smoky Mountains National Park. This system has been described by
Brown et al. (1979).
19
-------
TABLE 2. SUMMARY OF ANALYSES OF ELEMENTS DETERMINED BY ICPES AND SSMS (mg/liter)
ro
o
Element
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Range
ND*
(0.380-0.030)
ND
(0.007-0.005)
(0.020-0.005)
ND
(13.5-0.53)
ND
(0.003-<0.001)
(0.005-<0.001)
(0.007-<0.001)
(0.17-0.05)
ND
Average
<0.00lt
0.111
<0.001
0.0054
0.010
0.001
2.09
<0.001
0.001
0.001
0.002
0.036
<0.010
Frequency
(in 13)
samples
0
13
0
5
13
0
13
2
7
7
9
12
0
Element
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
Range
(1.19-0.12)
(0.12-0.002)
(0.001-<0.001)
(0.001-<0.001)
ND
ND
ND
ND
(0.054-0.006)
(0.004-<0.001)
ND
ND
0.014
Average
0.32
0.021
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.014
0.002
<0.001
<0.002
0.014
Frequency
(in 13
samples)
13
13
2
3
0
0
0
0
13
6
1
0
1
* ND signifies the element was Not Detected in any sample
t Values shown as "less than" (<) are detection limits
-------
TABLE 3. SUMMARY OF ANALYSES OF ELEMENTS DETERMINED BY
SSMS ONLY (mq/liter)
Frequency
Element Range Average (in 13 samples)
Ce
Rb
Br
Ga
Sc
K
S
P
Na
F
0.001-<0.001
0.003-0.001
0.04-<0.001
0.05-<0.001
0.002-<0.001
0.9-0.1
2-0.1
0.02-0.003
6-0.2
0.01-0.001
<0.001
0.002
0.010
0.001
0.001
0.38
0.48
0.011
1.2
0.003
1
13
12
10
6
13
13
13
13
12
The mercury air traps and the associated analytical methods used
indicated that mercury levels were not above background.
The charcoal filters were operated for the purpose of detecting organics
in air. Only two of the charcoal cartridges were analyzed for organics.
These samples included:
I.D. No. Location
3C-3 Uplands Field Research Station
(Gatli nburg, Tennessee)
1C-4 Ocanaluftee River
(Cherokee, North Carolina)
Operating Time (hrs) Volume
24 314 ms
9.9 125.2 m3
The samples were prepared and analyzed as follows. The charcoal was
removed from the metal canisters, placed in a flask, and shaken vigorously
with 100 ml of petroleum ether. The sample was filtered with the petroleum
ether concentrated by nitrogen blown down to 5 ml. The granules were then
placed in another flask and shaken vigorously with carbon disulfide. Again
the sample was filtered and the extract concentrated to 5 ml. The samples
were then analyzed by gas chromatography using a 63-Ni detector.
The results are shown in Table 5 and in Figures 7 and 8 for the petroleum
ether extraction only. Compound identifications were not performed, but the
21
-------
ro
TABLE 4. RESULTS OF MULTIELEMENT ANALYSES USING ICPES AND SSMS FOR
GREAT SMOKY MOUNTAINS UATER SAMPLES (mg/liter)
El ement
Silver
Al umi num
Arsenic
Boron
Barium
Beryllium
Calcium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Magnesium
Manganese
Molybdenum
Nickel
Lead
Antimony
Selenium
Tin
Strontium
Titanium
Vanadium
Ytterbi urn
Zinc
1
ICPES
<.002
.043
<.05
<.005
.005
<.002
.93
<005
<.005
<.005
<.005
.014
.01
.2
.002
<.01
<.005
<.05
<.010
<.05
<.05
.008
<.005
<.005
<.002
<.005
2A
SSMS
<.001
.03
<.001
*
.004
<.001
.5
<.001
.001
<.003
.001
.01
**
.2
.006
<.001
.001
<.001
<.001
<.001
<.001
.004
<.001
.001
***
.001
ICPES
<.002
.053
<.05
.007
.008
<.002
1.77
<.005
<.005
<.005
<.005
.009
.01
.34
.003
<.01
<.005
<.05
<.010
<.050
<.050
.018
<.005
<.005
<.002
<.005
SSMS
<.001
.040
<.001
it
.004
<.001
2.5
<.001
.003
.001
.001
.02
**
.3
.003
<.001
<.001
<.001
<.001
<.001
<.001
.02
<.001
<.001
***
.001
Sample Number
2B 3
ICPES
<.002
1.77
<.05
.012
.016
<.002
3.76
<.005
<.005
<.005
<.005
.018
.01
1.5
1.36
.014
.018
<.05
<.010
<.05
<.05
.025
<.005
<.005
.011
.075
SSMS
<.001
1.0
<.001
*
.007
<.001
2.5
<.001
.008
.001
.004
.02
**
1.0
2.0
.007
.03
<.001
<.001
.003
<.001
.03
<.001
.001
***
.04
ICPES
<.002
.18
<.05
.005
.006
<.002
.92
<.005
<.005
<.005
<.005
.034
.01
.25
.038
<.01
<.005
<.05
<.010
<.050
<.050
.006
<.005
<.005
<.002
<.005
SSMS
<.001
.4
<.001
*
.002
<.001
1.2
<.001
<.001
<.001
.001
.02
**
.2
.05
.009
<.001
<.001
<.001
<.001
<.001
.005
<.001
<.001
***
<.001
4
ICPES
<.002
.042
<.05
<.005
.013
<.002
1.36
<.005
<.005
<.005
<.005
.005
.01
.23
.004
<.01
<.005
<.05
<.010
<.050
<.050
.012
<.005
<.005
<.002
<.005
5
SSMS
<.001
.04
<.001
*
.02
<.001
1.0
<.001
<.001
.005
<.001
<.001
**
.2
.002
<.001
.001
<.001
<.001
<.001
<.001
.008
.003
<.001
***
<.001
ICPES
<.002
.030
<.05
<.005
.006
<.002
.56
<.005
<.005
<.005
<.005
.02
<.01
.12
.003
<.01
<.005
<.05
<.010
<.050
<.050
.006
<.005
<.005
<.002
<.005
SSMS
<.001
.07
<.001
*
.002
<.001
.2
<.001
<.001
<.001
.004
.01
**
.2
.009
<.001
<.001
<.001
<.001
<.001
<.001
.003
.002
<.001
***
<.001
6
ICPES
<.002
.078
<.05
<.005
.016
<.002
2.85
<.005
<.005
<.005
<.005
.005
<.01
.84
.12
<.01
<.005
<.05
<.010
<.050
<.050
.024
<.005
<.005
<.002
.014
SSMS
<.001
.04
<.001
*
.01
<.001
2.0
<.001
.002
.001
<.001
.005
**
1.0
.1
.001
<.001
<.001
<.001
<.001
<.001
.02
.004
<.001
***
.005
* Samples prepared in glass
** Not reported by SSMS
*** Internal standard
(continued)
-------
TABLE 4. (Continued)
ro
CO
Element
Silver
Al umi num
Arsenic
Boron <
Barium
Beryllium
789
ICPES SSMS ICPES SSMS ICPES SSMS
<.002 <.001 <.002 <.001 <.002 <.001
.13 .2 .052 .08 .05 .09
<.05 <.001 <.05 <.001 <.05 <.001
.005 * <.005 * .005 *
.014 .01 .007 .005 .007 .007
<.002 <.001 <.002 <.001 <.002 <.001
Calcium 13.5 17.0 .80 .60 1.15 1.0
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Magnesium
Manganese
Molybdenum
Nickel
Lead
Antimony
Selenium
Tin
Strontium
Titanium
Vanadium
Ytterbium
Zinc
<.005 <.001 <.005 .001 <.005 <.001
<.005 .003 <.005 <.001 <.005 <.001
<.005 .003 <.005 .003 <.005 <.001
<.005 .005 <.005 <.001 <.005 .004
.11 .3 .023 .03 .025 .02
<.010 ** <.010 ** <.01 **
1.19 1.0 .14 .4 .22 .5
.015 .02 .006 .01 .003 .007
<.010 <.001 <.010 <.001 <.01 <.001
<.005 .001 <.005 <.001 <.005 .001
<.05 <.001 <.05 <.001 <.05 <.001
<.01 <.001 <.01 <.001 <.01 <.001
<.05 <.001 <.05 <.001 <.05 <.001
<.05 <.001 <.05 <.001 <.05 <.001
.054 .09 .008 .007 .009 .003
<.005 .001 <.005 <.001 <.005 .004
<.005 .004 <.005 <.001 <.005 <.001
<.002 *** <.002 *** <.002 ***
<.005 <.001 <.005 <.001 <.005 <.001
Sample Number
10 11
ICPES
<.002
.072
<.05
<.005
.010
<.002
.94
<.005
<.005
<.005
<.005
.008
<.010
.18
.003
<.010
<.005
<.05
<.01
<.05
<.05
.008
<.005
<.005
<.002
<.005
SSMS
<.001
.04
<.001
*
.01
<.001
.5
<.001
.002
.002
.007
.01
**
.3
.002
<.001
<.001
<.001
<.001
<.001
<.001
.01
.002
<.001
***
<.001
ICPES
<.002
.044
<.05
<.005
.01
<.002
1.07
<.005
<.005
<.005
<.005
.031
<.01
.16
.002
<.01
<.005
<.05
<.01
<.05
<.05
.01
<.005
<.005
<.002
<.005
SSMS
<.001
.04
<.001
*
.02
<.001
1.0
<.001
<.001
<.001
.001
.07
**
.3
.002
<.001
<.001
<.001
<.001
<.001
<.001
.008
<.001
<.001
***
<.001
12
ICPES
<.002
.046
<.05
<.005
.006
<.002
.82
<.005
<.005
<.005
<.005
.005
<.01
.22
.002
<.01
<.005
<.05
<.01
<.05
<.05
.006
<.005
<.005
<.002
<.005
SSMS
<.001
.08
<.001
*
.002
<.001
.7
<.001
.001
.002
.002
.002
**
.5
.002
<.001
<.001
<.001
<.001
<.001
<.001
.009
.002
<.001
***
<.001
13
ICPES
<.002
.38
<.05
<.005
.002
<.002
.53
<.005
<.005
<.005
<.005
.005
<.01
.15
.031
<.01
<.005
<.05
<.01
<.05
<.05
.005
<.005
<.005
<.002
<.005
SSMS
<.001
.3
<.001
*
.008
<.001
.4
<.001
.003
<.001
.004
.001
**
.1
.05
<.001
<.001
<.001
<.001
<.001
<.001
.002
<.001
<.001
***
<.001
14
ICPES
<.002
.3
<.05
<.005
.02
<.002
.72
<.005
<.005
<.005
<.005
.17
<.01
.15
.05
<.01
<.005
<.05
<.01
<.05
<.05
.01
<.005
<.005
<.002
<.005
SSMS
<.001
.3
<.001
*
.05
<.001
.5
<.001
<.001
<.001
<.001
.1
**
.3
.05
<.001
<.001
<.001
<.001
<.001
<.001
.02
<.001
<.001
***
<.001
* Samples prepared in glass
** Not reported by SSMS
*** Internal standard
-------
6 3.
TABLE 5. SUMMARY OF RETENTION VOLUMES (cc) FOR "Ni GAS CHROMATOGRAPHIC
ANALYSES OF CHARCOAL FILTER SAMPLES NO. 1C-4 AND 3C-3
(Petroleum Ether Extracts)
Instrument
Parameters
Column temperature = 55°C
Detector temperature = 272°C
Column temperature = 104°C
Detector temperature = 273°C
Column temperature = 151°C
Detector temperature = 273°C
Column temperature = 190°C
Detector temperature = 276°C
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
1
2
3
4
5
6
7
8
9
10
1
2
3
4
5
6
7
1
2
3
4
5
6
7
8
9
Retenti on
3C-3
(North Side)
• « •
50
70
100
110
—
150
160
300
370
___
20
30
40
50
___
120
160
220
—
10
20
40
60
110
—
160
___
20
30
70
—
___
___
—
Volume (cc)
1C-4
(South Side)
30
40
50
—
___
___
120
150
___
___
370
10
20
30
40
___
60
120
__-
—
230
10
20
40
60
___
150
— -
6
20
30
70
100
130
150
210
320
24
-------
Column Temperature 190°C
Detector Temperature 276°C
Attenuation 32 x 102
63Ni Detector
o
a
CO
o
+*
o
«
O
Time
Figure 7- Chromatogram of petroleum ether extract of sample 3C-3,
25
-------
Column Temperature 190°C
Detector Temperature 276°C
Attenuation 16 x 102
63Ni Detector
Time
Figure 8. Chromatogram of petroleum ether extract of sample 1C-4,
26
-------
comparisons of peaks between samples taken from the two sides of the park are
of particular interest as shown in Table 5. All samples had a 2-yl injection
volume, chart speed was 2 min/cm, and carrier gas flow was 50 ml/min.
No attempt was made to identify the individual peaks. It is assumed most
of the organics detected are of natural origin. Considerably more research
and developmental effort is required before identification of airborne
anthropogenic organics in background areas such as the Great Smoky Mountains
can be accomplished.
In summary, the compounds detected at each site have either identical
retention volumes or very similar retention volumes. Large differences in
retention volumes occurred only when the column temperature was raised to
190°C.
VEGETATION AND LITTER
The vegetation was analyzed by the University of California's (UCLA)
Laboratory of Nuclear Medicine and Radiation Biology. This analytical
technique has been previously described by Alexander et al. (1975).
Vegetative standards obtained from the U.S. Bureau of Standards with
certified trace element levels were submitted as quality assurance samples.
Based upon the results of these standards, expected precision limits were
calculated for this analytical technique. The precision limits are presented
as follows:
Elements
K, Ca, Mg, Cu, Mn, B, Sr, Ba, Al
P, Na, Zn, Fe, Cr, Ag, Ti, V
Li, Pb
Minimum detection limits are:
Maximum Allowable % Deviation
From a Known Value or COV of Replicates
±20%
±40%
±50%
Element
P
Na
K
Ca
Mg
Zn
Cu
Fe
Mn
ppm
50.0
1.0
150.0
1.0
50.0
5.0
0.2
0.6
0.1
Element
B
Al
Si
Ti
V
Co
Ni
Mo
Cr
ppm
0.2
0.1
1.0
0.5
1.0
1.5
0.5
0.2
0.2
Element
Sr
Ba
Li
Ag
Sn
Pb
Be
Cd
ppm
0.2
0.2
0.3
0.1
0.3
1.0
0.2
3.0
These limits and precision values were accepted by the investigators,
27
-------
The data for trace element values in vegetation and forest litter by site
are summarized in Tables 6 through 17. The purpose in sampling vegetation
was to obtain an estimate of field sampling error and to begin to define the
possible use of certain types of vegetation for biological monitors.
Estimates of field sample error can be used to determine the number of
samples required to reach a certain level of confidence. With the amount of
data presented in Tables 6 through 17, it was not feasible to make this
calculation for each sample type/element combination. The coeffients of
variation are shown in Table 18 for certain elements found in vegetation.
With the exception of manganese and aluminum most of the coefficients of
variation range between 10 and 30 percent.
Arbitrarily, a desired sampling error of plus or minus 10 percent at the
95 percent confidence level was chosen. For example, if witch hobble, shown
in Table 18 above, were chosen as a sample species and strontium as the
element, it would be necessary to collect approximately 23 samples. Similar
estimates can be made for all species and elements. During field sampling
and analysis, the number of samples used would probably be controlled by the
sample/element combination with the greatest variability tempered by the
resources available.
For samples that exhibit a large coefficient of variation such as the
manganese in rhododendron, the number of samples required to meet precision
levels as stated would be approximately 100. A decrease in precision of only
2 percent would reduce the number of samples required to 71. Our conclusion
concerning the required number of vegetation samples for a biosphere reserve
monitoring system is that the number required for our desired confidence
level is reasonable, and a cost-effective system can be designed.
Another consideration in determining the number of samples collected is
the interaction of analytical error with field sampling error. All
vegetation and litter samples in this study were analyzed in triplicate and
replicated nine times on each sample site. With this type of design,
analysis of variance techniques to determine the variability from the
analytical error versus that from field sampling was accomplished (Snedecor,
and Cochran 1967). The estimated variance of the sample mean per
determination is given by the mean square between blocks (i.e., sites 11, 12,
13, and 14) divided by the total number of determinations. This in turn can
be partitioned into the various components that contribute to this variance
of the individual sample mean per determination. For example, for cobalt in
forest litter, 2.2 percent of the variation per determination is due to
analytical error, 11.1 percent is due to subsamples from within each site,
and 86.7 percent is due to variation between the sites. For lead in forest
litter, the estimated variance of the sample mean per determination is broken
into the following relative contributions: 1.9 percent from analytical
error, 7.4 percent from variability within a block, and 90.7 percent from
variability between sites. In spite of the fact that the precision limits of
acceptance for lead are plus or minus 50 percent, this is an example that, as
large as the analytical error may be, the field error is much greater.
Therefore, to reduce field study error and to increase the reliability of
estimating trace element levels, more effort should be expended on collecting
28
-------
TABLE 6. SUMMARY OF TRACE ELEMENT VALUES IN FOREST LITTER FROM SITE 11
ro
vo
Concentration of Trace Element (ppm) in Subsamples*
i ffs-
Element
, y
A1 umi num
Barium
Beryllium
Boron '
Cadmium
Calcium
Chromiumm
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium (%)
Silicon (%)
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
1
5883
188
0.6
32.2
ND
680
14.9
1.5
18.4
5560
217
2.0
1397
320
1.4
16.7
1877
0.52
6.0
ND
1290
31.6
<0.3
786
11.4
25.4
2
9587
309
0.6
14.6
ND
1419
35.4
2.1
38.8
6653
191
5.3
2970
2220
2.7
31.2
3323
2.27
8.1
ND
2330
40.7
0.3
1590
17.3
10.7
3
8773
196
0.5
17.0
ND
172
11.1
1.0
25.6
7043
279
4.7
2190
1095
2.2
12.3
1370
3.05
10.0**
ND
2050
17.3
<0.3
1707
17.9
5.5
4
16433
208
1.2
13.5
ND
72
27.7
2.6
40.1
11367
314
11.6
5290
850
5.1
25.8
<50
7.70
8.9
ND
3330
15.9
0.4
2373
27.6
<5.0
5
8800
325
0.4
9.6
ND
304
18.2
1.5
25.2
6633
266
2.5
1787
286
2.2
17.8
853
1.29
9.5
ND
746
44.0
1.3
1513
16.7
12.6
6
4857
140
<0.2
13.3
ND
513
5.1
1.5
24.7
5893
181
1.4
1303
227
0.8
9.4
<50
0.06
4.3
ND
150
29.5
<0.3
508
5.9
36.7
7
9167
281
0.8
11.5
ND
420
15.3
1.5
23.5
7000
323
4.1
1987
326
2.3
16.4
1910
1.73
6.6
ND
646
35.4
0.8
1463
15.6
5.6
8
5590
168
<0.2
10.2
ND
1290
7.7
1.9
24.7
6123
212
1.9
1160
340
1.1
12.6
<50
0.14
4.6
ND
186
40.6
0.6
666
8.0
37.6
9
4263
181
0.5
10.1
ND
1507
5.6
1.5
26.1
5427
231
1.9
927
320
0.9
9.1
<50
0.09
4.5
ND
150
49.8
0.5
465
6.0
48.0
X
8150
222
0.5
14.6
ND
708
15.6
1.7
27.1
6855
246
3.9
2119
664
2.1
16.8
1037
1.87
7.0
ND
1210
33.8
0.4
1230
14.0
20.3
* except for
** llnnor limit
potassium
• nf Hpt.pr.1
and sil
•.inn
icon
ND = Not Detected
-------
TABLE 7. SUMMARY OF TRACE ELEMENT VALUES IN NETTLE LEAVES FROM SITE 11
CO
o
Element
Concentration of Trace Element (ppm) in Subsamples
345678
Al umi num
Barium
Beryl 1 i urn
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
6090
435
ND
25.6
ND
14800
ND
16.9
3890
ND
5.5
8890
1060
ND
9.5
5340
12800
78100
0.2
6190
104
ND
1630
32.0
806
180
ND
40.6
ND
25000
ND
9.3
309
ND
5.5
3916
228
ND
1.9
2220
41500
2780
0.4
90.8
112
ND
48.9
43.3
1860
250
ND
44.0
ND
21900
ND
15.6
848
ND
2.9
5883
342
ND
1.8
2400
37100
6650
0.4
117
133
ND
216
28.1
2960
261
ND
84.5
ND
18800
ND
14.5
1780
ND
3.3
6480
808
ND
8.5
4240
43100
20500
0.5
414
90.4
ND
613
69.5
3020
242
ND
41.9
ND
20100
ND
10.5
1800
ND
3.4
6780
493
ND
3.6
3650
55000
21500
0.3
334
109
ND
642
26.4
1601
244
ND
45.4
ND
25500
ND
10.1
911
ND
3.0
9440
374
ND
2.8
1650
48700
6670
0.3
103
167
ND
146
52.2
1460
238
ND
39.4
ND
24200
ND
9.7
657
ND
2.7
8680
554
ND
2.3
1500
45800
4550
0.4
84.4
175
ND
99.5
53.6
2140
145
ND
38.3
ND
17800
ND
12.6
1490
ND
3.0
6150
437
ND
3.0
2180
65600
5770
0.4
128
106
ND
313
32.5
572
288
ND
39.6
ND
28700
ND
12.2
538
ND
3.6
7260
267
ND
1.7
2000
57500
3640
0.3
86.3
148
ND
91.4
30.0
2370
254
ND
44.4
ND
21900
ND
12.4
1360
ND
3.7
7050
507
ND
3.8
2800
45200
16700
0.3
839
127.3
ND
421.8
40.8
ND = Not Detected
-------
TABLE 8. SUMMARY OF TRACE ELEMENT VALUES IN RHODODENDRON LEAVES FROM SITE 11
Element
Concentration of Trace Element (ppm) in Subsamples
345678
Aluminum
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodium
Strontium
Tin
Titanium
Vanadium
Zinc
234
186
ND
25.1
ND
14700
0.2
ND
7.9
85.7
<1.0
0.4
2260
1390
ND
1.1
838
14200
314
0.7
88.3
48.2
0.3
5.3
2.2
18.1
200
157
ND
24.6
ND
14100
0.2
ND
5.0
83.7
<1.0
0.4
2410
1210
ND
<0.5
984
12200
277
0.6
33.7
24.7
<0.3
5.6
2.1
16.1
212
210
ND
20.6
ND
13300
0.2
ND
5.2
80.4
<1.0
0.6
2020
1840
ND
0.8
920
9750
239
0.8
59.1
30.3
0.5
4.1
2.1
13.9
225
198
ND
27.8
ND
14100
0.3
ND
5.8
93.2
4.9
0.5
2330
1770
ND
2.6
813
5740
209
0.9
57.5
51.7
1.1
3.5
2.3
13.0
755*
319
ND
28.2
ND
18000
1.0
ND
7.5
367
<1.0
1.0
3730
2470
ND
0.7
645
10700
2473*
1.1
97.1
73.4
0.6
54.7*
2.6
12.6
342
279
ND
28.3
ND
18500
0.7
ND
5.3
105
1.8
0.9
2930
2700
ND
0.6
699
8550
497
1.0
23.9
64.7
0.9
9.3
1.3
12.3
331
270
ND
29.8
ND
15600
0.8
ND
7.5
134
<1.0
0.9
3310
2460
ND
1.4
820
11900
378
1.0
81.7
66.2
1.1
12.0
1.4
12.0
419
228
ND
24.8
ND
12500
0.8
ND
67
186
6.6
0.5
2230
1260
ND
2.3
446
8180
576
0.9
89.9
59.9
1.4
16.7
2.0
10.9
313
213
ND
26.8
ND
15100
0.8
ND
7.7
139
<1.0
1.0
3000
2350
ND
1.5
674
13700
452
1.1
91.4
56.6
1.1
12.8
1.3
8.4
337
229
ND
26.2
ND
15100
0.6
ND
6.5
142
1.5
0.7
2690
1940
ND
1.3
759
10500
601
0.9
69.1
52.8
0.8
13.8
1.9
13.0
* Possibly contaminated with soil
ND = Not Detected
-------
TABLE 9. SUMMARY OF TRACE ELEMENT VALUES IN FOREST LITTER FROM SITE 12
CO
ro
Element
Concentration of Trace Element (ppm) in Subsamples
345-678
Aluminum
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
9983
277
0
7
ND
358
43
1
27
5997
275
6
1777
598
2
38
466
3
9
ND
3890
30
1
2000
13
<5
.6
.6
.6
.5
.7
.0
.6
.5
.33
.8
.1
.0
.3
.0
9057
341
1.0
13.7
ND
1533
49.0
2.6
24.7
6907
356
5.8
1640
1180
2.5
43.6
3030
1.57
7.6
ND
2140
49.7
2.1
1281
13.6
13.1
9643
213
0.7
8.7
ND
163
53.0
1.5
26.6
5710
259
8.9
2473
769
2.9
45.3
1620
5.53
10.0*
ND
4760
19.1
1.7
2130
15.4
<5.0
17167
285
0.8
17.4
ND
1.0
40.4
3.3
33.2
10030
399
17.4
3600
1310
5.4
39.4
560
10.55
10.0*
ND
5390
19.5
0.4
2453
39.0
<5.0
9863
222
0.2
- 17.9
ND
207
29.8
2.1
18.1
8127
294
9.0
1967
845
2.5
280
<50
2.87
10.0*
ND
3430
22.8
1.1
1643
18.8
15.9
10336
224
0.4
16.5
ND
692
33.7
2.4
27.1
8057
308
10.4
2417
1129
2.5
32.8
<50
1.97
9.1
ND
2640
31.9
1.7
1467
17.1
10.9
12066
229
0.3
7.3
ND
96.0
68.7
4.1
36.4
9473
288
12.3
2873
1613
4.2
59.4
<50
6.50
9.8
ND
3620
15.4
3.3
2343
29.0
«5.0
9740
241
1.0
10.4
ND
1054
38.6
1.7
36.4
4740
263
6.9
2187
224
2.5
33.3
<50
3.95
10.0*
ND
2180
36.7
0.3
1199
8.8
16.5
10600
133
1.2
12.6
ND
335
31.0
1.7
41.1
7977
290
9.4
2870
385
3.7
31.8
11100
4.62
10.0*
ND
2610
16.7
0.1
1603
16,8
14.0
10940
241
0.7
12.5
ND
493
43.1
2.3
30.2
7446
303
9.6
2423
895
3.2
39.1
2036
4.53
9.6
ND
3410 /
26.9
1.3
1791
19.0
7.8
* Upper machine limit
ND = Not Detected
-------
TABLE 10. SUMMARY OF TRACE ELEMENT VALUES IN RHODODENDRON LEAVES FROM SITE 12
CO
Element
Concentration of Trace Element (ppm) in Subsamples
345678
Al umi num
Bari.um
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodium
Strontium
Tin
Titanium
Vanadium
Zinc
251
336
ND
17.8
ND
16700
0.4
ND
4.5
75.9
4.5
0.9
2320
1440
ND
1.9
498
5400
250
0.9
48.2
44.7
0.7
8.4
1.5
5.5
305
319
14.6
16300
0.4
5.9
119
2.8
1.5
2940
3230
ND
1.5
720
8910
355
1.3
28.9
57.7
1.4
10.2
1.2
5.0
429
343
12.5
17200
0.7
5.8
188
2.0
1.5
3130
2710
ND
2.0
216
7950
788
1.2
50.9
52.9
1.2
17.7
1.6
<5.0
196
359
25.6
16200
0.2
5.8
69.1
1.8
1.3
2670
2060
<0.5
1005
5160
162
0.8
84.0
36.8
1.5
8.4
1.2
15.1
283
213
18.8
15000
0.4
5.9
80.5
1.4
1.8
2040
634
<0.5
861
7850
296
0.7
91.8
35.8
0.5
6.8
2.7
13.1
277
202
19.1
17200
0.6
6.2
75.2
<1.0
1.7
2230
1300
<0.5
798
6170
272
0.8
79.1
36.5
0.6
6.3
2.3
5.7
447
317
21.0
17500
0.6
6.0
150
<1.0
1.3
2750
1820
<0.5
687
8100
658
0.8
72.1
55.3
0.7
22.1
1.8
10.0
383
340
24.7
17900
2.3
11.9
118
<1.0
1.2
2440
2130
1.1
746
7660
591
0.9
71.0
71.4
1.3
14.2
2.1
9.0
320
318
21.0
16900
0.4
5.0
92.8
<1.0
1.4
2600
2010
<0.5
717
6210
364
0.8
52.4
66.1
0.7
8.9
1.8
10.1
321
305
19.4
16800
0.7
6.3
107
1.5
1.4
2570
1930
0.9
694
7050
415
0.9
64.3
50.8
1.0
11.4
1.8
8.5
ND = Not Detected
-------
TABLE 11. SUMMARY OF TRACE ELEMENT VALUES IN CHRISTMAS FERN FROM SITE 12
CO
Element
Al uml num
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
1
786
86.8
ND
10.4
ND
2850
ND
ND
4.1
174
ND
0.6
2430
149
ND
3.4
304
13400
702
0.4
28.3
34.2
ND
6.8
ND
11.8
2
451
60.9
8.8
1620
3.3
45
0.4
2790
172
3.4
672
8730
156
0.3
<1.0
25.0
0.9
14.6
Concentration of
3 4
694
111
12.7
4960
7.4
100
0.7
3050
173
3.2
964
20400
266
0.4
<1.0
39.0
4.5
17.9
683
152
17.6
8650
7.2
126
0.9
3010
191
2.9
980
23900
416
0.4
<1.0
51.7
2.8
22.3
Trace El
5
617
117
12.0
6450
5.4
84.8
0.8
3380
169
3.0
591
19600
525
0.3
<1.0
42.8
9.7
17.8
ement (ppm) in Subsamples
678
509
101
9.6
3490
4.9
57.0
0.7
3010
165
3.2
617
17300
167
0.3
<1.0
28.8
6.1
16.8
784
129
12.4
5290
4.9
121
0.8
2580
185
4.2
569
14100
679
0.5
25.9
44.0
2.0
9.8
820
88.7
14.1
3360
4.6
79.6
3.9
2700
199
3.7
519
21200
219
0.4
<1.0
34.7
8.2
12.9
9
471
85.8
6.1
2070
4.1
31.2
0.7
3230
142
3.6
588
14500
74.2
0.4
<1.0
30.3
3.7
7.4
X
646
103
11.5
4300
5.1
91.1
0.7
2780
172
3.1
645
17000
356
0.4
6.0
36.7
4.7
14.5
ND = Not Detected
-------
TABLE 12. SUMMARY OF TRACE ELEMENT VALUES IN FOREST LITTER FROM SITE 13
CO
tn
Element
Concentration of Trace Element (ppm) in Subsamples
345678
Al umi num
Barium
Beryllium
Boron
Cadmi urn
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon*
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
7893
180
0.8
15.5
ND
851
12.3
1.5
30.8
6560
424
3.7
1150
261
2.0
13.1
1740
0.64
7.3
ND
696
26.7
1.2
857
11.2
52.6
8527
222
0.6
21.0
ND
92
14.7
1.5
19.0
5486
459
4.8
1327
200
1.9
15.1
1033
1.18
7.9
ND
1720
21.4
2.2
1400
13.7
12.4
7123
208
0.4
13.7
ND
200
15.4
1.5
18.1
4256
479
4.5
1143
232
1.5
15.7
226
0.96
7.7
ND
1830
24.5
2.3
1073
12.4
12.4
5553
199
0.3
31.7
ND
232
6.1
1.5
15.9
3847
378
4.0
934
165
1.1
7.3
250
0.56
4.4
ND
622
19.2
1.6
869
11.5
17.3
7873
189
0.3
15.9
ND
371
10.5
1.5
20.8
6463
453
5.0
1277
274
1.7
13.1
<50
0.55
7.1
ND
1120
22.9
2.0
961
13.4
17.9
8703
262
0.2
13.6
ND
132
13.7
2.4
22.7
7847
477
5.0
1647
244
2.2
14.9
<50
1.12
6.8
ND
1940
23.3
2.0
1330
15.1
6.3
8903
229
0.2
5.6
ND
151
13.5
2.0
22.3
5813
397
4.8
1813
256
1.8
15.4
<50
1.17
7.5
ND
2580
25.9
1.1
1196
14.0
9.3
9713
254
3.9
8.9
ND
28
20.4
1.0
26.6
6373
610
3.8
2130
227
2.8
20.3
11740
2.45
8.7
ND
3000
14.6
<0.3
1811
14.8
8.2
12667
332
5.3
28.0
ND
7
29.3
0.5
25.0
8453
879
6.1
3413
278
3.8
29.8
22433
5.37
10.0
ND
5850
20.8
<0.3
2780
17.0
14.4
8461
230
1.3
17.1
ND
229
15.1
1.5
22.3
6122
506
4.6
1648
237
2.1
16.1
4158
1.55
7.5
ND
2150
22.1
1.4
1364
13.7
16.8
* Upper machine limit
ND = Not Detected
-------
TABLE 13. SUMMARY OF TRACE ELEMENT VALUES IN FOREST LITTER FROM SITE 13
CO
en
Element
Aluminum
Barium
Beryllium
Boron
Cadmi urn
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
1
539
230
ND
30.2
ND
14400
ND
ND
7.7
191
ND
<0.3
2730
2540
ND
3.6
1880
7600
708
0.9
86.8
56.9
ND
18.3
ND
46.5
2
766
181
24.9
5370
7.4
293
<0.3
3520
1070
1.7
1450
27300
1810
0.3
85.1
29.5
22.8
73.8
Concentration of
3 4
403
188
18.6
5830
6.4
118
<0.3
3760
1240
2.4
978
22700
301
0.7
73.7
22.9
4.4
47.3
560
172
19.8
7770
5.9
194
<0.3
3550
592
2.8
802
26500
494
0.6
72.8
27.4
14.6
44.2
Trace Element (ppm) in Subsamples
5678
466
169
19.0
5510
6.4
180
<0.3
3430
1040
3.6
853
19600
607
0.7
76.7
26.1
12.0
56.3
432
181
20.0
5880
6.4
151
<0.3
3320
1030
3.4
945
26000
359
0.6
71.6
28.6
7.8
31.0
581
194
21.1
4450
5.7
150
<0.3
3450
312
3.2
536
17300
2780
0.5
75.1
31.3
7.5
39.5
572
222
21.9
6400
6.1
139
<0.3
2770
613
3.3
805
19900
1440
0.6
78.2
31.0
7.5
48.8
9
500
165
18.2
6220
5.3
150
<0.3
3490
611
4.2
563
19900
690
0.6
73.3
30.5
9.9
49.2
X
535
189
21.5
6870
6.4
174
<0.3
3340
1000
3.4
978
20800
1020
0.6
77.0
31.6
11.6
48.5
ND = Not Detected
-------
TABLE 14. SUMMARY OF TRACE ELEMENT VALUES IN WITCH HOBBLE FROM SITE 13
OJ
Element
Concentration of Trace Element (ppm) in Subsamples
345678
Al umi num
Barium,
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodium
Strontium
Tin
Titanium
Vanadium
Zinc
598
242
NO
28.6
ND
13300
0.2
ND
6.1
212
1.2
1.8
4300
1760
ND
<0.5
1220
4140
1440
0.8
67.1
69.3
1.1
24.3
2.3
66.1
975
204
ND
18.1
ND
5450
<0.2
ND
6.5
430
<1.0
0.7
4160
635
ND
1.0
279
24200
8110
0.6
59.3
31.8
0.3
29.3
2.2
56.4
464
304
ND
27.0
ND
16100
0.4
ND
10.3
164
5.5
2.0
3400
2560
ND
<0.5
1297
8470
565
1.1
86.7
64.8
0.9
16.1
2.3
61.2
613
286
ND
27.7
ND
15100
0.4
ND
9.1
180
7.3
1.7
2600
2490
ND
0.8
1463
10700
589
1.1
76.5
58.8
0.8
19.5
2.4
41.3
559
271
ND
22.5
ND
13800
0.5
ND
5.8
165
6.7
1.3
3170
2280
ND
<0.5
979
6460
596
1.2
56.3
47.8
0.4
17.0
2.4
33.5
592
301
ND
26.9
ND
14500
0.5
ND
8.0
229
<1.0
1.7
2780
1710
ND
0.7
1042
3160
1140
0.8
76.6
73.9
0.3
20.4
2.5
25.9
655
258
ND
23.8
ND
11700
0.3
ND
8.2
244
3.7
1.8
2880
1770
ND
0.5
878
8310
765
0.9
96.5
52.7
0.3
27.6
1.9
49.1
707
252
ND
28.8
ND
12700
0.2
ND
10.0
239
<1.0
1.9
2510
1910
ND
1.4
1323
12300
825
0.9
88.9
56.7
0.3
22.7
2.6
31.0
771
252
ND
35.7
ND
14300
0.5
ND
10.1
298
<1.0
2.0
2960
1640
ND
0.9
813
15400
1490
0.8
81.1
77.0
<0.3
34.3
2.2
35.0
659
263
ND
26.6
ND
13000
0.3
ND
8.2
240
2.7
1.6
3200
1860
ND
0.7
1033
10400
1730
0.9
76.5
59.2
0.5
23.5
2.3
44.4
ND = Not Detected
-------
TABLE 15. SUMMARY OF TRACE ELEMENT VALUES IN FOREST LITTER FROM SITE 14
CO
00
Element
Concentration of Trace Element (ppm) in Subsamples
345678
Al umi num
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
8310
258
2
12
ND
750
22
3
31
10710
463
10
2717
1727
3
25
1834
1
8
ND
830
21
0
2457
22
60
.0
.3
.5
.2
.4
.4
.2
.6
.47
.7
.7
.8
.1
.8
15267
272
2.0
19.2
ND
908
16.3
8.2
54.1
11560
466
15.3
6497
4207
6.2
23.3
1650
3.44
9.8
ND
5070
42.5
<0.3
1263
14.1
19.0
5707
351
0.3
8.3
ND
6080
18.8
2.5
20.1
4966
106
3.7
2070
1250
1.0
20.8
1250
0.34
4.9
ND
307
76.5
<0.3
548
6.5
17.4
5267
335
<0.2
6.6
ND
1240
12.1
4.2
20.8
7426
183
3.4
1733
1239
1.1
18.5
<50
0.16
5.0
ND
421
57.0
0.8
567
7.6
19.0
10363
211
1.2
5.4
ND
137
20.4
2.2
29.7
7700
320
8.2
2507
1197
2.6
24.3
1757
2.02
10.0*
ND
648
18.1
0.6
1873
14.6
3.3
8480
334
0.8
8.8
ND
515
11.5
3.4
19.2
7370
353
5.5
1640
932
1.8
17.1
953
0.85
7.1
ND
295
47.8
1.4
1360
12.2
29.6
6510
299
0.2
5.6
ND
753
13.9
3.6
16.4
5600
195
3.9
1513
755
1.4
18.6
<50
0.62
4.8
ND
216
41.8
1.4
850
9.1
6.5
11700
282
0.5
13.7
ND
634
31.2
5.1
40.8
10140
225
13.1
4673
2527
3.5
33.3
<50
2.81
9.7
ND
3450
33.5
1.8
2017
13.7
6.7
4887
191
0.9
9.0
ND
3690
7.9
1.5
21.7
5230
119
3.5
1723
719
0.9
17.1
715
0.27
4.4
ND
378
68.4
<0.3
708
4.7
42.0
8499
282
0.9
9.9
ND
1634
17.2
3.8
28.3
7856
270
7.4
2793
1616
2.4
22.1
907
1.33
7.2
ND
1290
45.3
0.8
1294
11.6
22.7
* Upper machine limit
ND = Not Detected
-------
TABLE 16. SUMMARY OF TRACE ELEMENT VALUES IN RHODODENDRON LEAVES FROM SITE 14
CO
vo
Element
Concentration of Trace Element (ppm) in Subsamples
345678
Al umi num
Barium'
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodium
Strontium
Tin
Titanium
Vanadium
Zinc
262
270
ND
14.4
ND
15200
0.3
ND
5.6
79.3
<1.0
1.4
1890
963
ND
<0.5
945
5430
300
0.5
22.1
51.8
<0.3
7.9
1.4
7.0
284
243
ND
19.0
ND
15800
0.2
ND
5.2
73.6
<1.0
1.7
2120
596
<0.5
824
3440
408
0.5
79.0
49.9
<0.3
8.8
2.0
11.7
429
237
ND
16.1
ND
15600
0.5
ND
5.5
131
<1.0
1.5
2150
954
<0.5
883
6560
882
0.5
74.0
78.7
<0.3
15.2
2.2
11.2
274
377
ND
12.7
ND
14800
0.4
ND
6.1
86.6
<1.0
1.6
3190
1460
<0.5
934
7570
384
0.7
23.9
117
<0.3
9.1
2.0
14.4
334
260
ND
16.8
ND
13500
0.2
ND
6.5
116
sl.O
<0.3
2270
1520
2.1
1203
8280
501
0.6
<1.0
93.7
<0.3
10.1
1.3
15.2
337
260
ND
20.7
ND
12100
0.2
ND
10.9
118
<1.0
<0.3
2510
2290
2.0
1587
13300
462
0.7
<1.0
117
<0.3
7.2
1.6
22.0
454
315
ND
24.5
ND
12900
<0.2
ND
8.2
185
<1.0
<0.3
2310 .
2110
2.2
1510
12300
711
0.7
<1.0
141
<0.3
13.7
1.3
17.4
464
272
ND
16.6
ND
14700
0.3
ND
5.0
154
<1.0
<0.3
2460
707
2.3
832
10100
912
0.5
42.8
66.9
<0.3
12.1
1.2
13.5
322
213
ND
15.8
ND
15200
0.2
ND
5.9
111
<1.0
<0.3
2360
658
2.8
965
10500
428
0.5
<1.0
61.0
<0.3
5.6
<1.0
15.5
351
271
ND
17.4
ND
14400
0.3
ND
6.5
117
<1.0
0.7
2360
1250
1.4
1075
8610
554
0.6
26.9
86.4
<0.3
10.0
1.5
14.2
ND = Not Detected
-------
TABLE 17. SUMMARY OF TRACE ELEMENT VALUES IN YELLOW BIRCH FROM SITE 14
Element
A1 umi num
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Silicon
Silver
Sodi urn
Strontium
Tin
Titanium
Vanadium
Zinc
1
568
281
ND
17.5
ND
16300
ND
ND
6.1
133
ND
0.7
2510
1220
ND
3.9
1390
12800
738
0.9
71.1
67.4
ND
13.2
ND
32.9
2
274
422
19.4
17100
8.1
115
1.0
2290
1220
4.8
1510
41500
576
0.9
73.6
93.8
13.1
35.7
Concentration of Trace Element (ppm) in Subsamples
345678
254
348
19.0
15800
5.2
117
0.8
2170
404
4.1
1200
37100
637
0.8
71.2
76.5
13.7
17.8
229
440
18.0
16000
6.0
116
1.4
3760
1990
2.6
2490
43100
827
0.9
79.2
123
10.1
105.9
178
295
24.1
14100
6.4
101
1.1
3170
1780
3.2
2220
55000
531
0.9
71.8
83.9
7.7
56.7
341
418
26.5
25800
8.2
144
1.8
5670
2400
2.5
2580
48700
2100
1.1
751
88.5
13.1
58.3
284
215
16.2
16800
*
4.7
111
1.1
2960
808
2.7
1500
13400
833
0.5
74.4
55.7
12.7
65.7
203
207
17.1
10700
6.0
117
0.8
25000
1750
4.0
1520
9710
1660
0.8
75.0
61.8
7.2
69.3
9
267
318
19.0
17100
7.4
128
1.7
3500
974
6.4
1150
20200
910
0.6
72.8
99.2
13.0
86.1
X
277
327
19.7
16600
6.4
120
1.1
3170
1390
3.9
1730
18900
979
0.8
73.8
83.3
11.5
58.7
ND = Not Detected
-------
TABLE 18. COEFFICIENTS OF VARIATION FOR ELEMENTAL LEVELS IN
VtGETATION SAMPLES COLLECTED IN THE GREAT SMOKY
MOUNTAINS BIOSPHERE RESERVE (%)
Elements
Sample
Rhododendron - site 11
Rhododendron - site 12
Rhododendron - site 14
Witch Hobble - site 13
Nettle - site 11
Christmas Fern - site 12
Wood Fern - site 13
Yellow Birch - site 14
Mn
21.4
13.5
15.3
20.5
27.2
18.5
10.6
34.2
Mg
38.5
39.8
50.4
30.9
54.2
10.8
64.6
45.4
Al
51.4
25.9
22.3
22.6
66.8
21.9
20.0
30.9
Sr
30.4
26.0
37.8
23.9
28.7
23.2
34.6
24.9
Ra
22.3
22.1
17.3
11.9
31.1
26.1
12.1
26.6
samples in the field and less on reducing or improving analytical precision.
Similar types of calculations were made for all elements in the forest
litter; however, no deviations from the above pattern were noted.
While this presampling of Great Smoky Mountains National Park was
originally designed as a pilot study for a larger project, the results for
lead in litter are of particular interest. Levels of lead in soil around
power plants range from 5 to 100 ppm (Lindberg et al., 1975; Wiersma and
Crockett, 1978). Linzon et al. (1976) reported an overall lead level in soil
of 292 ppm in urban areas near a secondary lead smelter. Gill et al. (1974)
reported lead levels ranging from 89.3 ppm to 1,403 ppm in soil collected in
five U.S. cities. The soil lead levels found in this study were relatively
low—15 to 20 ppm—while the lead levels in litter are comparable to lead
concentrations found in soil in urban areas.
Sites 11, 12, and 14 are located at relatively low altitudes—near
1,000 m—while site 13 is located at a high altitude—approximately 2,000 m.
The lead levels in litter for sites 11, 12, and 14 range between 246 to 303
ppm, whereas the average lead level at the high altitude site, site 13, was
506 ppm. An analysis of variance indicated a significant difference among
the four sites at the 99 percent confidence level. An orthogonal comparison
confirmed that the lead contamination at site 13 was significantly higher
than at sites 11, 12, and 14.
These data are very similar to data reported by Reiners et al. (1975) for
the White Mountains of New Hampshire. They reported that lead levels in the
litter layer increased with altitude until the Krumholz Forest was reached,
where a slight decrease in concentration occurred. The lead levels in the
41
-------
White Mountains ranged from 35 to 336 ppm, with the fir forest sites having
the highest concentrations.
The lead found in the Great Smoky Mountains appears to be from nonnatural
sources. Lead levels in soils collected beneath the litter layer are not
excessively high. Translocation of lead in vegetation is minimal, and only
small amounts of lead were detected in the vegetation sampled. The
vegetation samples were collected from the understory. The majority of the
litter comes from the overstory canopy (Lutz and Chandler, 1961), which could
be an effective filter for airborne lead particles. The air samples did not
collect lead; however, the limit of analytical detection was fairly high—50
ng/mj. Also rain could wash considerable quantities of lead from the air
(Schlesinger et al., 1974). Therefore, it is unlikely that the high levels
of lead detected in the litter are part of natural lead sources, but rather
reflect deposition of lead from outside sources. Similar conclusions were
made by Reiners and his research associates (Reiners et al. 1975).
There is some indication that certain plants may be better pollutant
accumulators than others. For example, witch hobble is the only understory
plant that shows lead residue. Also its average content of elements that may
be associated with entrapped dust, such as aluminum and silica, are at least
twice as high as those values for rhododendron. This could be related to
leaf morphology. Witch hobble has a large broad leaf with a rough surface.
Rhododendron leaves are elongated, with a fairly large surface area but a
shiny, smooth surface. The results are too preliminary to draw more than an
indication of the possible selection of witch hobble as a biological monitor.
Other parameters need addressing, such as uptake and translocation, before
definite conclusions can be made.
SOIL ANALYSES
Sample preparation included adding 25 ml of concentrated nitric acid to a
10-g aliquot of oven-dried soil. After digestion for a 24-hour period, the
soil was separated from the supernatant by centrifugation and filtration and
washed three times with distilled deionized water. The supernatant and
washes were combined in a volumetric flask and diluted to 100 ml. In
addition to the soil extracts, distilled water blanks, acid blanks,
standards, and spiked standards were analyzed in duplicate for zinc, lead,
copper, cadmium, manganese, and lithium. The analyses were accomplished by
standard techniques using a Perkin-Elmer 603 Atomic Absorption
Spectrophotometer.
The results are summarized in Table 19. A slight increase in soil lead
is present at site 13. The high cadmium level for site 13 is the result of
two samples that, when analyzed, gave a high value for cadmium. The quality
assurance samples, analyzed simultaneously with the field samples, gave no
reason to reject the two high cadmium samples.
42
-------
TABLE 19. RESULTS OF SOIL ANALYSES FOR GREAT SMOKY MOUNTAINS (yg/g)
Cadmium
Copper
Lead
Lithium
Manganese
Zinc
Site 11
1.0
5.7**
18.0
9.8
190.2
36.0
Site 12
0.9
4.3**
15.0
8.9
223.7
34.0
Site 13
3.0*
4.3
20.0
4.3
39.9
21.0
Site 14
0.8
11.9
15.0
17.7
486.9
63.0
* Two very high values were detected (14.1 and 9.2 yg/g). When not
included, mean cadmium levels for site 13 are 0.5 yg/g.
** Single analysis
43
-------
REFERENCES
Ad Hoc Task Force on GNEM. 1970. A global network for environmental
monitoring. A Report to the Executive Committee, U.S. National Committee
for the International Biological Program. Ad Hoc Task Force on GNEM.
Anas, R. E., and A. J. Wilson. 1970. Organochlorine pesticides in nursing
fur seal pups. Pestic. Monit. J. 4_(3) :114-114.
Alexander, G. V., D. R. Young, D. J. McDermott, M. J. Sherwood, A. J. Mearns,
and 0. R. Lunt. 1975. Marine organisms in the southern California
bight as indicators of pollution. International Conference on Heavy
Metals in the Environment, Toronto, Canada, pp. 955-972.
Brown, K. W., G. B. Wiersma, and C. W. Frank. 1979. Monitoring Device for
Sampling Air in Remote Areas. U.S. Environmental Protection Agency, Las
Vegas, Nevada. (In Press).
Chow, T. J., and J. L. Earl. 1970. Lead aerosols in the atmosphere:
increasing concentrations. Science. 169;577-580.
Dzubay, T. G., and R. K. Stevens. 1975. Ambient air analysis with
dichotomous sampler and X-ray fluorescence spectrometer. Environ. Sci.&
Techno!. i(7):663-668.
Elgmork, K., A. Hagen, and A. Langeland. 1973. Polluted snow in southern
Norway during the winters 1968-1971. Environ. Pollut. £:41-52.
Franklin, J. F. 1976. The conceptual basis for selection of United States
biosphere reserves and features of established areas. Presented at the
U.S.-U.S.S.R. Symposium on Biosphere Reserves, May 5 and 6, Moscow,
U.S.S.R.
Franklin, J. F. 1977. The biosphere reserve program in the United States.
Science 195:262-267.
Gill, J. A., A. E. Carey, G. B. Wiersma, H. Tai, and T. J. Forehand. 1974.
Heavy metal levels in soils of five U.S. cities, 1972. Presented at the
Annual Meeting of the American Society of Agronomy, Chicago, IL.
Hirao, Y., and C. C. Patterson. 1974. Lead aerosol pollution in the High
Sierra overrides natural mechanisms which exclude lead from a food chain.
Science ,184:989-992.
44
-------
Jaklevic, J. M., F. S. Goiilding, B. V. Jarrett, and J. D. Meng. 1973.
Applications of X-ray fluorescence techniques to measure elemental
composition of particles in the atmosphere. 166th American Society
Meeting on Analytical Methods Applied to Air Pollution Measurements,
Dallas, TX, April 8-13.
Jaklevic, J. M., B. W. Loo, and F. S. Goulding. 1976. Photon induced X-ray
fluorescence analysis using energy disperive detector and dichotomous
sampler. X-Ray Fluorescence Analysis of Environmental Samples Symposium,
Chapel Hill, NC, January 26-28.
Johnson, N. M., R. C. Reynolds, an G. E. Likens. 1972. Atmospheric sulphur:
its effect on the chemical weathering of New England. Science
177:514-516.
Lazarus, A. L., E. Lorange, and J. P. Lodge. 1970. Lead and other metal
ions in United States precipitation. Environ. Sci. & Techno!.
£(l):55-58.
Lingberg, i>. E., A. W. Andren, R. J. Raridon, and W. Fulkerson. 1975. Mass
balance of trace elements in Walker Branch watershed: relation to
coal-fired steam plants. Environ. Health Perspectives 12:9-18.
Linzon, S. N., B. L. Chai, P. J. Temple, R. G. Pearson, and M. L. Smith.
1976. Lead contamination of urban soils and vegetation by emissions from
secondary lead industries. J. and Air Poll. Cont. Asso. 26:(7):650-654.
Long, S. J., D. R. Scott, and R. J. Thompson. 1973. Atomic absorption
determination of elemental mercury collected from ambient air on silver
wool. Anal. Chem. 45(13):2227-2233.
Lutz, H. J., and R. E. Chandler. 1961. Forest Soils, New York, NY.
Man and Biosphere. 1974. Programme on man and the biosphere (MAB). Task
Force on Pollution Monitoring and Research in the Framework of the MAB
Programme Organized Jointly by UNESCO and UNEP. Final Report. MAB
Report Series No. 20, Moscow, U.S.S.R.
Massachusetts Institute of Technology. 1970. Man's impact on the global
environment, assessment and recommendations for action. Massachusetts
Institute of Technology Press, Cambridge, Massachusetts, 319 pp.
Munn, R. E. 1973. Global environmental monitoring system (GEMS) action plant
for phase I. SCOPE Report No. 3, International Council of Scientific
Unions.
Reiners, U. A., R. H. Marks, and P.M. Vitousek. 1975. Heavy metals in
subalpine and alpine soils of New Hampshire. Oikos 26(3):264-274.
45
-------
Schlesinger, W. H., W. A. Reiner, and D. S. Knupman. 1974. Heavy metal
concentrations and deposition in bulk precipitation in montane ecosystems
of New Hampshire, U.S. Environ. Poll tit. £: 39-47.
Snedecor, G. W., and W. G. Cochran. 1967. Statistical Methods. 6th
Edition, Iowa State University Press, Ames, Iowa, 593 pp.
Weiss, H. V., M. K. Koide, and E. D. Goldberg. 1971. Mercury in a Greenland
ice sheet: evidence of recent input by man. Science 74:692-694.
Wiersma, G. B., K. W. Brown, and A. B. Crockett. 1978. Development of a
Pollutant Monitoring System for Biosphere Reserves. EPA-600/4-78-052.
U.S. Environmental Protection Agency, Las Vegas, Nevada, 124 pp.
Wiersma, G. B., K. W. Brown, and A. B. Crockett. 1977. Development of a
Pollutant Monitoring System for Biosphere Reserves and Results of the
Great Smoky Mountains Pilot Study. Presented at the 4th Joint Conference
on Sensing of Environmental Pollutants, New Orleans, LA.
Uiersma, G. B., and A. B. Crockett. 1978. Trace elements in soil around the
Four Corners powerplant. EPA-600/3-78-079. U.S. Environmental
Protection Agency Report, Las Vegas, Nevada, 18 pp.
Zoller, W. H., E. S. Gladney, and R. A. Duce. 1974. Atmospheric
concentrations and sources of trace metals at the South Pole. Science
183:198-200.
46
-------
APPENDIX
SCIENTIFIC NAMES OF PLANTS USED IN THIS REPORT
Beech
Black cherry
Christmas fern
Fraser fir
Hem!ock
Magnolia
Nettle
Red spruce
Rhododendron
Sugar maple
Tulip poplar
Witch hobble
Wood fern
Yellow birch
Fag us grandifolia
Prunus serotina
Polystichum acrosticoides
Abies fraseri
Tsuga canadensis
Magnolia fraseris
Laportea canadensis
Picea rubens
Rhododendron spp*
Acer saccharum
Liriodendron tulipifera
Viburnum alnifolium
Dryopteris campyloptera
Betula allegheniensis
47
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPOR
iRT NO.
EPA-600/4-79-072
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
iREAT SMOKY MOUNTAINS PRELIMINARY STUDY FOR
BIOSPHERh RESERVE POLLUTANT MONITORING
5. REPORT DATE
November 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
6. B. Wiersma, R. W. Brown, R. Hermann,
C. Taylor and J. Pope
8. PERFORMING ORGANIZATION REPORT NO.
I. PERFORMING ORGANIZATION NAME AND ADDRESS
Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Las Vegas, NV 89114
10. PROGRAM ELEMENT NO.
XH1627J
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency-Las Vegas, NV
Office of Research and Development
Environmental Monitoring Systems Laboratory
Las Vegas, NV 89114
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/07
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
A presampling of physical and biological media at preselected locations on the
Great Smoky Mountains Biosphere Reserve was completed. The media collected, which
included air, water, soils, litter, and various plant species, were used to determine
elemental concentrations and to help in the design of an efficient and cost-effective
monitoring system.
The results showed that air concentrations of trace elements were below detectable
limits. Indications of organic air contaminants were evident.
A number of compounds such as zinc, toluene, and methylene chloride were found
in water. In addition, dimethyl hexene, ethyl benzene, and phthalate esters are
suspected water contaminants.
Analytical results of the vegetation, soils, and litter showed a variety of
elemental contamination. The concentration of lead in the litter layer at four
sampling sites ranged from 246 to 469 ppm. These data, similar to those reported
by other researchers showed that lead levels increased with altitude.
Based upon a field sampling error of plus or minus 10 percent at the 95 percent
confidence level, the number of samples required to satisfy this condition, based
upon the samples/element combination, was calculated.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
environmental biology
site survey
pollution
Biosphere Reserves Great
Smoky Mountains
soils
pi ants
water
air
06F
08G
08H
21. NO. OF PAGES
56
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
o US. GOVERNMENT PHINTING OFFICE: 1879—683-282/2211
------- |