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9700 SouthCassAvenue,Argonne,Illinois60439
Acknowledgments ........................................................................................ vi
Abstract .................................................................................................... 1
1 Introduction ........................................................................................... 1
2 Background ...........................................................................................
7 References ............................................................................................ 66
2 Location of the Three Training Ranges Selected for Investigation at GTA .......... 13
4 TCLP Limits for Heavy Metals and the Minimum Soil Concentrations
Needed to Yield a Hazardous TCLP Classification ....................................... 9
Tables (Cont.)
15 XRF Lead Readings and Corresponding ICP-AES Lead Values for Two Soil
Samples Collected from Range 124 at GTA during July 1992 ........................ 56
Dean Bass, Edmund Huff, and Lynn TenKate, Argonne National Laboratory, Chemical
Technology Division/Analytical Chemistry Laboratory, for providing the analyses of soils by the
inductively-coupled plasma atomic-emission spectroscopy method;
John Taylor, Melvin Findlay, Nancy Tomczyk, and Laura Skubal, Argonne National
Laboratory, Reclamation Engineering and Geosciences Section analytical laboratory, for sample
processing, analyses of soils by the toxic characterization leaching procedure, and analyses of
vegetation and water samples;
Sandra Spurgash, Argonne National Laboratory, Environmental Research Division, for the
analyses of soils for explosives using high-pressure liquid chromatography; and
Department of the Army, U.S. Army 7th Army Training Center, 100th Area Support
Group, Directorate of Engineering and Housing, Environmental Division, for providing the
necessary funding for the study.
Heavy-Metal Contamination on Training Ranges
at the Grafenw6hr Training Area, Germany
Large quantities of lead and other heavy metals are deposited in the
environment of weapons ranges during training exercises. This study was
conducted to determine the type, degree, and extent of heavy-metal contamination
on selected handgun, rifle, and hand-grenade ranges at Grafenw6hr Training Area,
Germany. Soil, vegetation, and surface-water samples were collected and analyzed
using the inductively-coupled plasma atomic-emission spectroscopy (ICP-AES)
method and the toxic characterization leaching procedure (TCLP). The ICP-AES
results show that above-normal levels of lead and copper are in the surface soil at
the handgun rang*,,high concentrations of lead and copper are in the berm and soil
surface at the rifle range, and elevated levels of cadmium and above-normal
concentrations of arsenic, copper, and zinc are present in the surface soil at the
hand-grenade range. The TCLP results show that surface soils can be considered
hazardous waste because of lead content at the rifle range and because of cadmium
concentration at the hand-grenade range. Vegetation at the handgun and rifle ranges
has above-normal concentrations of lead. At the hand-grenade range, both
vegetation and surface water have high levels of cadmium. A hand-held X-ray
fluorescence (XRF) spectrum analyzer was used to measure lead concentrations in
soils in a field test of the method. Comparison of XRF readings with ICP-AES
results for lead indicate that the accuracy and precision of the hand-held XRF unit
must improve before the unit can be used as more than a screening tool. Results of
this study show that heavy-metal contamination at all three ranges is limited to the
surface soil; heavy metals are not being leached into the soil profile or transported
into adjacentareas.
1 Introduction
Military training exercises during the past several decades at the Grafenwtihr Training Area
(GTA) have included firing of a variety of weapons and weapon systems on a number of firing
ranges and target areas. The types of weapons used during these live-fire exercises range from
small arms and hand grenades to artillery, tanks, and helicopter gunships. One environmental
consequence of these firing exercises is the deposition of potentially large quantities of heavy
metals (e.g., lead, copper, zinc) and explosive residue onto the soils of firing ranges and target
areas at GTA. Thus, elevated concentrations of some heavy metals and explosive residue may be
present in these soils. It is also conceivable that some heavy metals could be incorporated into
food webs through uptake by vegetation. Equally important, it is possible, given certain
circumstances, that significant quantities of heavy metals could be introduced into the local surface
waters and/or leached from the soil into groundwater supplies. These conditions could provide an
effective mechanism for transporting heavy metals to surrounding nonmilitary areas, producing
significant adverse environmental impacts affecting the local German population. The type,
degree, and extent of heavy-metal and explosive-residue contamination from current and past
training exercises need to be determined, and the probability of off-site transport of heavy-metal
contaminants must be evaluated.
This investigation was undertaken to provide the U.S. Army with documentation on the
type, degree, and extent of heavy-metal and explosive-residue contamination on three types of
training ranges and their environs at GTA in Germany. Current and past training exercises
requiring the use of small arms and other munitions have resulted in the deposition of heavy metals
onto the soils of training ranges. Potential contamination of the local environment by the
introduction of heavy metals into the local surface waters or groundwater supplies was assessed.
2 Background
The metals inventoried in this investigation are arsenic (As), barium (Ba), cadmium (Cd),
chromium (Cr), cobalt (Co), copper (Cu), lead (Pb), mercury (Hg), nickel (Ni), tin (Sn), and zinc
(Zn). All of these metals, with the exception of barium, meet the definition of a heavy metal: a
metallic element with a specific gravity of 5.0 g cm -3 or more that is generally toxic in relatively
low concentrations to plants and/or humans and animals. These heavy metals were inventoried
because they are present in various components of small-arms ammunition or hand grenades.
The three training ranges at GTA selected for investigation were a handgun range
(Range 122), a rifle range (Range 124), and a hand-grenade range (Range 111). Range 122 is
used for handgun practice primarily by military police units, and Range 124 is used by combat
units for checking the accuracy of the sights on their rifles. Both Ranges 122 and 124 are
considered small-arms ranges. The following information on the chemical composition of small-
arms ammunition is from Heath et al. (1991). A typical round of small-arms ammunition consists
of a bullet or ball and a cartridge case containing the propellant and ignition cap. Bullets are either
solid or filled (with tracer or incendiary materials) and may or may not have an outer metal jacket.
The bullet is usually made of a lead alloy consisting of copper, sometimes tin, and up to 15%
antimony, which is added for hardness. Unjacketed or bare balls are used in several types of
revolver cartridges. Jacketed bullets are used in high-velocity and automatic weapons. The metal
jacket consists of either copper-plate or a thin layer of gilding metal having copper and zinc as the
major components. Bullets at high-velocity may shatter upon impact, exposing the lead, copper,
zinc, and antimony of the bullet core and jacket. Tracer munitions are used to determine the
direction of rapid fire. Tracer materials are made from compounds containing strontium,
magnesium, barium, zinc, and potassium. The ignition cap or primer for small-arms ammunition
generally contains compounds of lead, barium, antimony, and potassium. Potential sources of
heavy-metal contamination in the soils at small-arms ranges consist of the heavy metals contained
in the bullet, bullet jacket, tracer materials, and primer.
Range I 11 at GTA is used for high-explosive hand-grenade training by U.S. and German
Army combat units. The U.S. Army M67 fragmentation hand grenade consists of the body, an
explosive charge, a delay fuse to detonate the explosive, and several safety devices. The grenade
is about 9 cm (3.5 in.) in length by 6.4 cm (2.5 in.) in diameter and has a total weight of
approximately 397 g (14 oz). The grenade body is a 6.4-cm (2.5-in.) diameter sphere made from
steel that is designed to burst into numerous fragments when the explosive is detonated. The body
of the grenade is filled with approximately 184 g (6.5 oz) of high explosive, Composition B,
consisting of 60% RDX (hexahydro-l,3,5-trinitro-l,3,5-triazine) and 40% TNT
(2,4,6-trinitrotoluene). Because Composition B is highly corrosive, the internal surface and
components of the grenade may be coated with cadmium or other metal alloys to prevent corrosion.
The fuse and primer contain lead azide, lead styphnate, and RDX. Safety devices consist of steel
pull ring, safety pin, and safety clip (Green 1992). Potential sources of heavy-metal contamination
in the soils at Range 111 consist of the explosive residue and the metals contained in the grenade
body, internal components and coatings, the fuse and primer, and safety devices.
All of the heavy metals included in this investigation occur naturally in most soils and are
taken up to some degree by plants. Cobalt, copper, and zinc are considered essential in the growth
and development of higher plants, and the other heavy metals may benefit normal plant growth if
available in very low concentration (Mengel and Kirkby 1978). All of these heavy metals, with the
exception of barium and mercury, are necessary in very small amounts for the normal growth of
humans and animals (Anke et al. 1984). The heavy metals included in this investigation are also
considered a health hazard if present and available in the environment at levels in excess of their
normal concentrations. Table 1 gives the average concentration of several heavy metals in soils,
the normal range of concentration in soils, and the normal range in plant leaves.
There is no evidence that arsenic is essential for plant growth, but stimulation of root
growth in solution cultures with the addition of small amounts of arsenic has been noted. Arsenic
can be toxic to plants, and arsenic compounds were commonly used as insecticides and herbicides
in agriculture until their replacement by organics (Lisk 1972). It has been reported that soil
productivity is reduced where arsenic from sprays has accumulated in orchard soils (Liebig 1966).
Arsenic has been added to the list of essential elements in the diet of mini-pigs, goats, and rats
(Anke et al. 1984). Both acute and chronic exposure to arsenic may cause poisoning in humans
and animals, but acute poisoning is rare today. Chronic poisoning usually results from exposure
to contaminated air or drinking water or ingestion of arsenic in drugs or food. Arsenic poisoning
among industrial workers is characterized by perforation of the nasal septum, skin changes, and
peripheral neuritis. There is also evidence that arsenic may cause lung cancer (Ishinishi et al.
Barium is not considered essential for plants or animals. It is not reported to be toxic to
plants, and the uptake of barium by plants does not correlate with the total amount in the soil
(Vanselow 1966a). Barium is toxic to humans and animals because all water- and acid-soluble
barium compounds are poisonous. Occupational poisoning by soluble barium salts is virtually
unknown, but accidental poisoning with barium-containing household and medical products has
been reported (Reeves 1986).
Cadmium is not an essential element for plants, and it can be toxic to plants, animals, and
humans. Some studies indicate plant growth is severely depressed with a relatively low
accumulation of cadmium in plants (Allaway 1968). New research suggests cadmium is essential
for rats and goats (Anke et al. 1984). Studies done in Japan indicate cadmium from polluted soils
and water can be incorporated into the food web in sufficient quantities to be toxic to humans
(Yamagata and Sigematsu 1970). Cadmium in the environment also has been implicated in human
hypertension and cardiovascular problems (Luckey et al. 1975).
There is no conclusive evidence that chromium is essential for plants, but plant-growth
stimulation in solution cultures with the application of low levels of chromium salts has been seen.
High levels of chromium in the soil can severely stunt or kill plants (Pratt 1966). Chromium is a
recent addition to the list of elements essential for humans and animals, but at high levels in the
diet, it can be toxic (Anke et al. 1984). Chronic exposure to chromate dust has been correlated
with lung cancer, and oral intake has been associated with growth depression and liver and kidney
damage in experimental animals (Anderson 1987).
TABLE1 Concentration
of Heavy Metalsin Soilsand PlantLeaves
It has been known for some time that cobalt is essential for microorganisms that fix
nitrogen in the nodules of legumes, but recent research indicates that it is also necessary for the
growth of higher plants (Mengel and Kirkby 1978). Results from other studies show that cobalt
can be toxic to plants when the concentration in the soil is relatively low (Vanselow 1966b).
Cobalt is an essential element for humans and animals because it is required for the production of
vitamin B12 (Baker and Chesnin 1975). Cobalt is not considered highly toxic to humans or
animals, but the addition of cobalt to beer has caused endemic outbreaks of cardiomyopathy among
heavy beer-drinkers, resulting in several fatalities. Animal studies also indicate cobalt may be a
carcinogen (Elinder and Friberg 1986).
Copper is an essential element for both plants and animals. A moderate deficiency of
copper in plants normally results in a reduction in growth or yield, while more acute deficiencies
cause dieback at terminal growth points. Excess copper also reduces growth and may cause iron
chlorosis symptoms resulting from a depression of the iron concentration in plant leaves. Copper
solutions were also used for herbicides and fungicides in agriculture until their replacement by
organics (Reuther and Labanauskas 1966). Copper is an essential element for humans and animals
because it is required for the function of several essential enzymes. Ingestion of a large amount of
copper salts causes gastrointestinal disturbances, and chronic copper exposure may cause liver and
kidney damage (Aasetil and Norseth 1986).
Lead is not considered an essential element for plant growth, and no cases of lead
deficiency in plants have been reported. Most observations of lead toxicity in plants are restricted
to water-culture experiments, where acute toxic effects result in a reduction in growth, but acute
toxicity is not generally seen in the field (Mengel and Kirkby 1978). Most research on lead in
humans and animals deals with the toxic effect of this element, but recent research indicates that
lead is essential in the diet of rats (Anke et al. 1984). Lead is a major pollutant in the environment,
and no other pollutant has accumulated in man to average levels so close to those which are
potentially clinically poisonous. One of the chief concerns of lead toxicity in humans is brain
damage to children. There is evidence that elevated lead levels in the environment can induce
aggressive behavior in animals. This evidence has implicated lead pollution as a causal factor for
the increased rate of delinquency in large industrial cities (Mengel and Kirkby 1978).
Mercury is not considered an essential element for either plants or animals. The amount of
mercury taken up by plants is small, and little is known about its reaction in the soil or its
relationship to plant growth. Mercury is known to undergo microbiological transformation to
methylmercury in the environment (Williams 1980). The hazards of long-term intake of
methylmercury are associated with its accumulation in the brain. Chronic poisoning resu',ts in
degeneration and atrophy of the sensory cerebral cortex and heating and visual impairment (Berlin
Nickel is found in most plants. It is not considered an essential element, and nickel
deficiency in plants has not been reported. Excess nickel produces a chlorosis in many plants that
resembles the symptoms of iron deficiency (Vanselow 1966c). Nickel is now considered an
essential element in the diet of chickens, rats, and goats (Anke et al. 1984). Dermatitis and lung
reactions in the form of asthma have been attributed to sensitization caused by nickel. There is also
evidence that some forms of nickel are carcinogenic (Norseth 1986).
Only limited information on tin in soils and plants has been published. There is no
evidence that it is essential or beneficial to plants, and it has not been shown to be detrimental to
plant growth under field conditions (Wallihan 1966). Relatively recent published information
indicates that tin is an essential element in the diet of animals (Anke et al. 1984). The toxicity of
tin after inhalation and ingestion is low, but acute gastrointestinal disturbances have been reported
following the ingestion of relatively large amounts (Magos 1986).
Zinc is an essential element for both plants and animals. One of the most common
micronutrient deficiencies in plants is zinc, and it is becoming increasingly significant in crop
production. Plants suffering from zinc deficiency often show chlorosis in the interveinal areas of
the leaf, and terminal growth is usually affected. An excess of zinc commonly produces iron
chlorosis in plants (Mengel and Kirkby 1978). Zinc is necessary for the function of various
enzymes in humans and animals. Symptoms and diseases related to zinc deficiency include acne,
poor wound healing, loss of taste and smell, and poor growth in children. Large oral doses of zinc
salts cause gastrointestinal disorders, but chronic zinc poisoning in humans has not been described
(Elinder 1986).
Because explosives such as TNT and RDX are the products of man, they do not occur
naturally in the environment. The production of TNT also results in a number of by-products,
including 2,4,5-TNT, 2,4-dinitrotoluene (DNT), and 2,6-DNT. Degradation of TNT in the
environment can result in the production of trinitrobenzene. Published information is limited on
explosives entering the food chain via plant uptake. Concentrations of TNT at 500 mg kg" 1 or
more in soils are generally toxic to many agricultural crops, and the uptake of TNT from the soil by
plants is low (Banwart and Hassett 1990). RDX in soils can be toxic to some agricultural crops,
but other crops can accumulate RDX in plant tissues to higher levels than the soil in which they are
growing (Banwart et al. 1991). Illness and death in munitions-plant workers from aplastic anemia
and toxic hepatitis have resulted from exposure to TNT. There is limited evidence that TNT is
carcinogenic, and much stronger evidence that dinitrotoluenes, especially 2,6-DNT, are
carcinogens. RDX can have adverse effects on the central nervous system and may produce
convulsion and/or unconsciousness following inhalation or ingestion (Rosenblatt et al. 1991).
Several national governments, including the United States, have developed guidelines
and/or regulations defining hazardous levels of heavy-metal contamination in soils and
groundwater. In 1988 the Netherlands published the "Dutch List" that gives concentrations for
three categories of heavy-met_ contamination: Category A-Baseline Concentration, Category B-
Detailed Investigation Needed, and Category C-Remedial Investigation Needed. As of this date,
Germany has not by national law established standard action or cleanup levels for heavy-metal-
contaminated soils and groundwater. However, the Bavarian state government has generally
adopted the Dutch List as a guideline for assessing heavy-metal contamination. The heavy-metal
concentrations in soil and groundwater listed for the three categories of the Dutch List are given in
Table 2 for the metals included in this investigation.
Because of the potential health hazard associated with heavy metals in the environment, the
World Health Organization has established guidelines for drinking-water quality that include
concentrations of some heavy metals. Although the heavy-metal concentrations suggested in these
guidelines are not established regulatory limits, these concentrations can be used to assess the
general surface-water quality. Table 3 lists the heavy metals included in this inventory and their
suggested maximum concentrations in drinking water.
Arsenic - 30 50 30 100
Barium 200 400 2,000 50 100 500
Cadmium 5 20 2.5 10
Chromium - 250 800 - 50 200
Cobalt 20 50 300 20 50 200
Copper - 100 500 50 2 00
Lead - 150 600 - 50 200
Mercury - 2 10 - 0.5 2
Nickel - 100 500 - 50 200
Tin 20 50 300 10 30 150
Zinc - 500 3,000 - 200 800
Concentration Concentration
Heavy Metal (rag L"1) Heavy Metal (mg L"1)
a NMCS = no max.,numconcentrationsuggested.
TCLP Limit Soil Concentration
TCLP Constituent (mg L"I) (mg kg-1)
The initial task of the investigation involved the selection of three typical small-arms ranges
at GTA. The three training ranges selected were a handgun range (Range 122), a rifle range
(Range 124), and a hand-grenade range (Range l 11). Background information on the physical
characteristics, training activities, and munitions used at each range was assembled. A literature
review was conducted to identify potential sources of heavy-metal and explosive-residue
contamination on each range. These data were used to develop a safety plan for the field sampling
During an initial field sampling effort, soil samples were collected from each of the three
ranges and analyzed at ANL to determine the type of heavy-metal and explosive-residue
contamination on each range. Analytical results for these soil samples were used to identify and
confirm the presence of contaminants. This information was used to develop a detailed sampling
plan for collecting the primary data and samples to assess the spatial distribution of heavy-metal
contaminants at each of the selected ranges. During the second field sampling effort, an X-ray
fluorescence spectrum analyzer was used to measure the concentrations of lead and other heavy
metals in the soils at the three ranges. Soil samples were collected at selected measurement
locations and analyzed at ANL to verify the field measurements made with the X-ray fluorescence
spectrum analyzer. Vegetation and surface-water samples were also collected at selected locations
and analyzed to assess heavy-metal contamination in the local environment.
Baltic Sea
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Portions of GTA have been used for military training activities since the early 1900s, when
the Bavarian Army established an artillery training range. The installation was used for training
German forces during both world wars and was acquired by the U.S. Army following World
War II. GTA is operated by the U.S. Seventh Army Training Command, headquartered at GTA,
and the current size of the installation is about 16,200 ha (40,000 acres). GTA is the major
U.S. Army training area in Europe for conducting live-fire training exercises, and the weapons
used during these exercises range from small arms and hand grenades to artillery, tanks, and
helicopter gunships.
The three small-arms training ranges at GTA selected for this investigation were a handgun
range (Range 122), a rifle range (Range 124), and a hand-grenade range (Range 111). These
three ranges were selected by ANL staff members and U.S. Army representatives at GTA because
they represent typical environmental conditions and different types of small-arms weapon-training
areas at GTA. Locations of the three ranges in GTA are shown in Figure 2.
Range 122 is used for handgun practice mainly by military-police units, and the range has
10 f'tring points with a 7-m (23-ft) high earthen berm located about 55 m (180 ft) from the firing
line. There are nine pop-up targets for each firing point: the first eight at distances ranging from
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10 m (32.8 ft) to 30 m (99 ft) and the ninth at 50 m (165 ft) from the firing line. A ditch that
runs parallel to the berm between the eighth and ninth targets is designed to remove runoff water
from the berm and range. The area around the targets is grass that is mowed short, and the ditch
and berm are covered with a mixture of grasses and low shrubs. There are a large number of spent
slugs on the soil surface behind the targets and on the berm. A tower behind the firing line is used
for observation and safety control during fLing exercises. The area on both sides and behind the
range is forested. The area directly behind the berm has tall grass and shrub cover and is part of
the GTA impact area. Range 122, as it exists now, was constructed about 10 years ago, but there
has been a small-arms range at this area for a number of years. Figure 3 shows the layout and
features of Range 122.
Range 124 is similar to Range 122 except that it is used by combat troops to check the
accuracy of their rifle sights before rifle qualification on another range. Range 124 has 10 pads
for firing from the prone position and 10 pits for firing from the standing position. There is a
single small fixed target 25 m (82 ft) from each firing pad, and the firing pits are located about
5 m (16.4 ft) behind each firing pad. The area between the firing pads and the targets is mowed
grass, and the 3-m (10-ft) high earthen berm generally lacks vegetative cover. There are no spent
slugs on the soil surface or evident in the berm soil, but there is a depression (bullet pocket) in the
berm behind each target. There is a shallow depression between the targets and the base of the
berm for drainage. A tower behind the firing line is used for observation and safety control during
range operations. The area behind the berm and to the right of the range is forested, and the
parking lot for Range 126 is to the left. Although there had been small-arms ranges in the area for
a number of years, the current Range 124 was constructed about 1977. Figure 4 shows the
layout and features of Range 124.
Range 111 is used to provide combat troops with practical experience in the use of high-
explosive hand grenades. This range consists of an open oval area about 50 m (165 ft) by 75 m
(245 ft) surrounded by an earthen berm approximately 1 m (3 ft) high. The area inside the berm
is barren and level except for a number of craters, up to 1 m (3 ft) in depth, resulting from grenade
detonations, and some of the deeper craters contain standing water. There are two concrete and
two log bunkers along the outer edge of the berm for the protection of the grenadier and the
instructor during training exercises. Several other larger concrete structures are located in the area
for the protection of troops during training exercises. There is some evidence of damage by
grenade fragments to the signs, structures, and trees outside the berm. The area outside the berm
has grass cover, and the surrounding area is forested. Figure 5 shows the layout and features of
Range 111, which was constructed about 1985.
The initial soil-sample collection was made at each of the three ranges during April 1992.
At Ranges 122 and 124, initial sampling locations were selected to represent different degrees of
suspected heavy-metal and explosive-residue contamination. Several soil samples were collected
from the berm directly behind targets (bullet pockets), while other samples were taken from other
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parts of the berm and from the area between the firing line and the targets. Additionalsamples
were collected from behind the fLringline and outside the area of training impacts to provide
backgroundconcentrationsof heavy metals in the native soils. All samples were collected by
means of a 2.5-cm (1-in.) soil probe from depths of 0-15 cm (0-6 in.) and 15-30 cm (6-12 in.).
The purposeof sampling at the 15-30 cm depth was to assess potential leaching of heavy metals
below the soil surface. A sedimentsample fromdrainageof each rangewas collected to assess the
transport of heavy metals into the adjacent environraent. A total of 15 samples were collected
fromeach of the two ranges.
At Range 111 (the hand-grenade range), 14 surface-soil samples were collected from
within the berm area. Only surface samples were collected because grenade fragments and
explosive residueswere notexpected to penetrate the soil to an appreciabledepth. These samples
were collected, by means of a stainless-steel spoon, at locations on the bottoms and sides of
grenade craters and from areas between the craters. Additional samples were collected from the
berm and from outside the berm to provide background levels of heavy metals in the native soil.
These background soil samples were collected from depths of 0-15 cm (0-6 it,.) and 15-30 cm
(6-12 in.) using the soil probe.
All samples were placed in precleaned, 250-mL, wide-mouth glass jars; the jars were
sealed in plastic bags, and the bagged jars packed in a cooler for transport to ANL. This packaging
was required to meet the U.S. Department of Agriculture (USDA) soil-import permit
requirements. The soil samples were analyzed at ANL to determine heavy-metal and explosive-
residue concentrations. Details of the methods used for these analyses are given in Section 4.4.
Analytical results from these samples were used to refine the primary data and sample collection
Primary data and sample collection was made during July 1992 according to the following
plan. At Range 122 (the handgun range), four sampling lines or transects were established.
Transects 1 and 2 ran perpendicular to the firing line, with transect 1 running from firing point 7
through the high impact area (bullet pocket) on the face of the berm and down the backside of the
berm. Data collection points were located at about 5-m (16.4-ft) intervals along this transect,
starting at the firing line. Other data collection locations were adjacent to this transect about 3 m
(9.8 ft) behind each of the eight pop-up targets. Transect 2 was also perpendicular to the firing
line, but this transect was located between firing points 5 and 6. Transect 2 also ran from the
firing line, through the target area, and down the backside of the berm. Data collection points on
this transect were located at about 5-m (16.4-ft) intervals, starting at the firing line. GTA
personnel, using a backhoe, excavated trenches about 1-m (3.28-ft) deep from the top to the base
of the berm adjacent to these two transects. These trenches provided access to the soil profile in
the berm for data and sample collection. The interval between data collection points along the
trenches was reduced to I m (3.28 ft) because of the potentially higher concentration of heavy
metals in the berm soil. Data collection points were located at 15-cm (6-in.) depth intervals on the
trench walls.
Two transects were also established parallel to the firing line at Range 122. Transect 3
was behind the eighth row of pop-up targets, 35 m (115 ft) from the firing line, and transect 4
was behind the last row of targets, 57 m (187 ft) from the firing line and about 3 m (9.8 ft) up
the base of the berm. The initial data collection points were established at the forest edge on the left
(south) side of the range, and additional points were established at about 5-m (16.4-ft) intervals
along these two transects. A control or background data collection point was established about
18 m (59 ft) behind firing point 7, in line with transect 1. A pit was excavated by the backhoe to
a depth of about 1 m (3.28 ft) to provide access to uncontaminated subsurface soil. Figure 3
shows the location of the transects and the background-data collection point at Range 122.
Transect locations and data and sample collection points established at Range 124 (the rifle
range) were similar to those at Range 122, except that six sampling transects were established at
Range 124. Transects 1 and 2 were located perpendicular to the firing line and extended across
the range, over the berm, and into the forest behind the berm. Transect 1 started at firing pad 5
and ran through the bullet pocket behind its single target, while transect 2 started between firing
pads 6 and 7. Trenches were excavated using a backhoe along these transects to provide access to
the subsurface of the berm (Figure 6). Data collection points were at intervals of about 5-m
(16.4-ft) along these transects except on the face of the berm along the trenches, where the interval
was 1 m (3.28 ft). As at Range 122, data collection points were established at 15-cm (6-in.)
depth intervals on the trench walls.
Four transects were established parallel to the firing line: transect 4, 1.5 m (4.9 ft) in
front of the firing pads; transect 5, 1.5 m (4.9 ft) in front of the firing pits; transect 6, 24 m
(79 ft) from the firing line and 1 m (3.28 ft) in front of the targets; and transect 7, 35 m (115 ft)
FIGURE 6 Excavation of the Trench in the Berm at Range 124at GTA during
July 1992
from the firing line and in line with the bullet pockets on the berm. The initial data collection point
on these transects was at the edge of the range on the left (south) side, and additional data
collection points were established at about 5-m (16.4-ft) intervals. A pit for the collection of
background data and samples was excavated adjacent to the forest edge about 20 m (66 ft) behind
firing pad 10. Figure 4 shows the location of the transects and the background-data collection
point at Range 124.
Because the physical layout of Range 111 (the hand-grenade range) is somewhat different
from that of Ranges 122 and 124, placement of the sampling transects was different. Transects 1
and 2 were parallel; each started at a bunker and extended to the berm on the other side of the open
area. Transects 3 and 4 were perpendicular to the initial transects, extending across the open area
from berm to berm starting at the left (east) berm. Data were collected at about 5-m (16.4-ft)
intervals along each transect, and no excavation was made in the berm. Background or control
sampling points were established in line with the transects, but 17 to 30 m (56 to 98 ft) beyond
the outer edge of the berm. Excavations for the collection of background data and samples were
done by hand. Figure 5 shows the location of the transects and background-data collection points
at Range 111.
Field measurements were taken at the data collection points using a portable energy-
dispersive X-ray fluorescence (XRF) spectrum analyzer. X-ray fluorescence is the production of
X-rays in the electron orbitals. In atoms that have many electrons, the electrons are arranged in
concentric shells at increasing distances from the nucleus. These shells are labeled K, L, M, N,
etc., with the K shell being closest to the nucleus. In the process of XRF, gamma photons
bombard the atom, and some of the gamma photons collide with the K- and L-shell electrons,
dislodging them from their orbits. This leaves a vacant space in the shell, which is immediately
filled by an electron from either the L, M, or N shell. The readjustment of the electrons is
accompanied by the enfission of an X-ray photon. The frequency (or energy) of the emitted X-ray
is characteristic of a specific element, and the quantity of X-rays emitted is proportional to the
concentration of that element.
FIGURE 7 Hand-Held XRF Unit and Soil-Sampling Supplies Used at GTA during July 1992
instrument is the manner of resolving the fluorescent X-ray spectrum emitted by the excited atoms
in the sample. A wavelength-dispersive instrument uses an optical assembly to sort the X-rays by
wavelength, while an energy-dispersive instrument uses an electronic detector that responds to the
energy of the X-ray being detected. Radioactive elements that produce a narrow band of
characteristic energies are commonly used in portable XRF instruments.
The instrument used during this investigation was the MAP XRF spectrum analyzer
produced by Scitec Corporation of Richland, Wash. This device contains a 0.025 Ci 109Cd
sealed source and was calibrated for lead in soil by the manufacturer. The detector is solid-state
silicon with an active area of 25 mm2. The detection limit for lead in soil for this device is
approximately 50 mg kg-1 using the standard 60-s measurement time. Detection limits for other
metals in soil are not available from the manufacturer.
The MAP XRF spectrum analyzer measures the spectrum of energies of X-rays emitted
from the sample. The spectrum of energies detected during a measurement is recorded, evaluated,
and saved in the memory of the instrument. These spectra can be copied to a portable computer
and analyzed at a later date to identify the presence of metals not targeted at the time of analysis.
The spectrum not only reveals this information about the sampie, but it gives the analyst data to
determine the nature of the soil matrix and to determine if the instrument is operating properly or if
the reading for the targeted element is being affected by interference.
A validation standard was run to assure that the instrument was operating properly in the
field. This validation standard was used to check the consistency of the device before use,
periodically during the day, and at the end of each day. Field measurements were made using a
60-s time period to collect the spectra. Data recorded in the XRF analyzer were transferred to a
portable computer, and backup copies of the data were made on a computer disk at the end of each
workday. All operators of the XRF analyzer used in this study have been trained and have
received certification from the manufacturer.
The procedure for taking measurements using the portable XRF spectrum analyzer
(Figure 8) was as follows. Before a measurement was made, vegetation was removed without
disturbing the soil surface, and a 60-s measurement was made in the cleared data collection point.
If the surface measurement indicated that lead was present at a level above the detection limit of the
instrument, several centimeters of soil were removed, and a second measurement was made on the
bottom of the excavation. If this reading also indicated that lead was present, additional soil was
excavated, and another measurement was made. This process was repeated until a reading below
the detection limit was observed. At a number of data collection points, representing a range of
lead concentrations in the soil, multiple readings were taken and used as replicates to determine the
precision of the device. The range number, transect number, location on the transect, depth of
reading, .,eplicate number, and lead concentration of each measurement were recorded in a
notebook. More than 200 XRF spectra were collected at Range 122, and at Range 124, over
165 XRF measurements were made. A majority of the XRF measurements taken at Range 111
were below the instrument detection limit for lead, and, as a result, only about 65 XRF readings
were taken at Range 111.
A total of 17 soil samples were collected from Range 122 at selected sampling points and
depths to confirm the XRF measurements. The soil samples were taken by means of a stainless-
steel spoon at locations representing high, intermediate, and below-detection or zero readings of
the XRF analyzer at a depth of about 5 cm (2 in.) below the soil surface. Each soil sample was
identified with the same identification information assigned to the XRF measurement taken at that
location. Soil samples were placed in precleaned, 250-mL, wide-mouth glass jars; the jars were
sealed in plastic bags; and the bags were packed in a coelcr for transport to ANL. This packaging
is required to meet the USDA soil-import permit requirements.
Five vegetation samples also were collected at Range 122 to determine the extent of heavy-
metal contamination in plant materials. Grass blades and/or other plant leaves were clipped from
the plant, with care taken to exclude root and soil materials, and the sample was placed in a
precleaned, 250-mL, wide-mouth glass jar. The jars were sealed in plastic bags and packed in a
cooler to meet the USDA vegetation-import permit requirements for transport. Vegetation samples
were collected adjacent to selected soil-sampling locations, and the identification assigned was
identical to the adjacent soil sample, with the exception of the depth designation.
A single water sample was collected from a pool of standing water in the drainage area at
the north end of the berm at Range 122. The water sample was collected in a precleaned, 250-mL,
wide-mouth glass jar, and care was taken to exclude bottom sediments. The acidity of the sample
was checked using standard pH paper, and nitric acid was added to acidify the sample to a pH of 2
or less. After acidification, the jar was sealed in a plastic bag and packed in a cooler for transport
to ANL.
The procedures for collecting soil and vegetation samples at Ranges 124 and 111 were the
sam:. zs those used at Range 122. At Range 124, a total of 30 soil and 8 vegetation samples
were collected. Due to the lack of standing water on or near Range 124, no water samples were
collected there. At Range 111, a total of 27 soil and 7 vegetation samples were collected.
Because of the lack of vegetation in the open area at Range 111, many of the vegetation samples
were taken on or outside the berm. Six water samples were collected from the standing water in
the craters in the open area at Range 111. These samples were collected using the procedures
previously described, and care was taken to exclude bottom sediments and soil from the sides of
the craters during collection.
Soil samples from both the initial and primary collections were analyzed in two different
laboratories at ANL using different procedures. The Analytical Chemistry Laboratory (ACL) at
ANL used the inductively coupled plasma-atomic emission spectroscopy (ICP-AES) procedure to
analyze the samp_'es for arsenic, barium, cadmium, chromium, cobalt, copper, lead, nickel, tin,
and zinc. Samples were digested according to EPA Method 3050A (Acid Digestion of Sediments,
Sludges, and Soils), followed by measurements according to EPA Method 6010 for ICP-AES
The digestion method consisted of heating 1-2 g of soil to 95°C in nitric acid and hydrogen
peroxide. The samples were then refluxed in hydrochloric acid, filtered, and diluted to 200 mL.
The ICP-AES procedure uses a two-point calibration, with standards prepared by dilution of
certified solutions. Measurements were made with an Instruments S.A., Inc., Model JY-86
spectrometer. This instrument consists of a 1-m JY-48 polychromator and a JY-38 scanning-
monochromator sequential-analysis system. Quality-control samples were run in accordance with
EPA methods. These methods included sample duplicates, laboratory control samples, spikes,
spike duplicates, postdigestion spikes, serial dilutions, and calibration verifications.
Mercury concentration in selected soil samples was determined at the ACL by cold-vapor
atomic absorption (CVAA) spectroscopy according to EPA Method 7471 (Soil) (EPA 1986).
Quality-control samples were run in accordance with EPA methods, which included spiked
samples, duplicate samples, and laboratory control samples.
The analytical laboratory of the Reclamation Engineering and Geosciences Section (RE&G)
of the Energy Systems Division at ANL analyzed selected soil samples using the toxic
characterization leaching procedure (TCLP). This EPA-approved method was used to characterize
the samples for barium, cadmium, chromium, copper, lead, tin, and zinc. Procedures for sample
preparation, determination of the appropriate extraction fluid, preparation of the extraction fluids,
and extraction of soil samples are from the (U.S.) 1990 Code of Federal Regulations. Samples
were allowed to air dry for about four days, and then they were crushed using a mortar and pestle
to pass a 6.35-mm (0.25-in.) sieve. Bullets and stones that would not pass the sieve were
removed. For selected samples, the bullets were returned to a portion of the original sieved sample
for another extraction and analysis to determine the amount of heavy metals contributed by a bullet
or bullet fragment.
2. Five grams of the ground sample is weighed into a 500-mL Erlenmeyer flask.
3. Reagent grade water (96.5 mL) is added, and the mixture is stirred for 5 min.
4. The pH of the mixture is measured and recorded. If the pH is <5.0, the sample
is extracted with fluid No. 1.
6. The mixture is heated to 50°C, held at 50°C for 10 min, and allowed to cool to
room temperature.
The two extraction fluids were prepared according to the following procedures; all
chemicals used, including water, were reagent grade.
The procedure for extraction of a soil sample with the extraction fluid was as follows:
2. The required quantity of extraction solution is added to the flask. This is equal
to 20 times the weight of the sample or 1,000 mL.
3. The flask is secured to a rotary agitator and rotated, end over end, at
30 revolutions per minute for 18 h. Temperature is maintained at 23°C.
Heavy-metal analysis of the TCLP extracts was performed using flame atomic absorption
(AA) spectroscopy, following the procedures given in Baker and Suhr (1982) and Franson (1989).
All AA analyses were performed on a Buck Atomic Absorption Unit, Model 200A. Quality
control in the RE&G laboratory was in accordance with the TCLP method described in the 1990
Code of Federal Regulations. These procedures require a duplicate extraction for every
8 samples, one blank extraction for every 10 samples, and one split analysis for every
10 extracts. One split was analyzed "as-is," while the other split was spiked with a mixed
standard. Concentrations in the spiked samples were in the midregion for the flame AA for each
metal and at least five times the detection limit for that metal.
Analysis for explosive compounds on selected soil samples from each of the three ranges
were performed at ANL. The method used employed an acetonitrile extraction followed by
analysis using high-pressure liquid chromatography (HPLC). This method is approved by the
U.S. Army Toxic and Hazardous Materials Agency and can be used to detect concentrations as
low as 1 mg kg-1 of TNT, RDX, and other explosives in soils (USATHAMA 1990).
Several physical and chemical characteristics also were determined in the RE&G laboratory
for selected soil samples from each of the three ranges. The characteristics measured and the
methods used were (l) soil pH, 1:1 in water (McLean 1982); (2) organic carbon by the Walkley-
Black method (Nelson and Sommers 1982); (3)cation exchange capacity of arid land soils
(Rhoades 1982); and (4) particle-size distribution by hydrometer (Gee and Bauder 1982).
The 20 vegetation samples collected during July 1992 were analyzed for barium,
cadmium, chromium, copper, lead, antimony, tin, and zinc content in the RE&G laboratory.
Samples were dried at 80"C, ground to pass a 0.8-mm (20-mesh) sieve, and representative 0.5 g
subsamples were weighed out for digestion. The wet-digestion procedure (Jones 1989) used
involves dissolving the plant materials with concentrated nitric acid, followed by repeated additions
of 30% hydrogen peroxide. The resultant solution is diluted to a known volume and analyzed for
the heavy metals using flame AA spectroscopy following the same procedures used for the TCLP
The seven water samples collected during July 1992 also were analyzed for barium,
cadmium, chromium, copper, lead, antimony, tin, and zinc in the RE&G laboratory. The water
samples were prepared using the nitric acid-sulfuric acid digestion as given in Franson (1989).
This digestion involves boiling a known volume of the acidified sample with small volumes of
concentrated nitric acid and sulfuric acid until the solution is clear. The resultant solution is cooled,
diluted to a known volume, and analyzed for heavy metals by using flame AA spectroscopy,
following the procedures used for the TCLP extracts.
The major objective of the analyses of the initial samples collected in April 1992 at GTA
was to verify the existence and relative levels of heavy metals and explosive residues on the three
training ranges. The history of the ranges and a review of the weapons used at the ranges were
considered in identifying potential pollutants. Analytical results of the heavy-metal concentrations
by the ICP-AES method for the initial soil samples are given in Table 5.
Only two samples for Range 122 have lead concentrations higher than the 150 mg kg -1
category B limit in the Dutch List, but both of these values are below the 600 mg kg-1
category C value. One of these samples is sediment from the drainage ditch, which suggests that
lead may be transported into adjacent areas with sediments. The other sample, from behind a
target, is higher also in copper than the 100 mg kg-1 limit for category B. The concentrations of
all the heavy metals in the other Range 122 samples are below their respective category B values.
These concentrations are generally within the normal range for heavy metals in soils (Table 1).
Data for Range 122 in Table 5 show relatively low levels of heavy metals, with only potential lead
and copper contamination.
Data in Table 5 for Range 124 show that all samples have lead concentrations higher than
the 600 mg kg -1 category C value. In fact, one bullet-pocket sample is over 12%
(126,000 mg kg -1) lead, while another sample, also from a bullet pocket, is almost 1.4%
(13,600 mg kg -1) lead. The berm-backside sample, taken at the 15-30 cm depth, and the
sediment sample also have lead levels higher than the category C limit. The elevated lead level in
the sediment sample, which is similar to the elevated lead level in the sediment sample from
Range 122, suggests that lead may be leaving Range 124 in sediments. Three of the six samples
also have copper levels higher than the 500 mg kg-1 category C value. Only the berm-backside
and sediment samples are below the 100 mg kg-1 category B value for copper. One bullet pocket
has an arsenic concentration higher than the 50 mg kg-1 category C value. This sample is also
higher than the 5 mg kg-1 category B value for cadmium and the 50 mg kg-1 category B value for
tin. Two other samples are higher in zinc than the 500 mg kg -1 category B value. Concentra-
tions of heavy metals from the other Range 124 samples are below the category B values and
generally within the normal range for soils (Table 1). Data for Range 124 samples in Table 5
show that lead, copper, arsenic, cadmium, tin, and zinc may all be pollutants of potential concern.
A review of the cadmium values given in Table 5 for samples from Range 111 suggests
that all the samples, except for the background sample, are higher than the 20 mg kg-1 cadmium
TABLE 5 Heavy-Metal Concentrations Determined by ICP-AES Method for Soils Collected at GTA during April 1992
122 S016 Behind target 0 - 15 BDLb 63.2 BDL 7.9 BDL 146 398 0.06 6.9 BDL 48.2
122 S017 Behind target 1 5-30 BDL 63.3 BDL 4.6 BDL 28.6 41.2 0.08 7.7 BDL 26.0
122 S022 Bullet pocket 0-1 5 BDL 83.4 9Di_ 3.0 BDL 57.0 123 0.06 4.9 BDL 23.8
122 S026 Berm 0-1 5 BDL 48.6 BDL 3.5 BDL 51.1 55.0 0.17 BDL BDL 30.2
122 S029 Background 1 5-30 BDL 71.6 BDL 5.5 BDL 23.7 31.6 0.06 11.5 1311 23.0
122 S030 Sediment Surface BDL 97.9 BDL 39.2 13.0 32.6 314 0.06 47.8 BDL 72.7
124 S003 Bullet pocket 0-1 5 19.4 51.8 1.2 7.5 BDL 271 7,870 0.06 7.3 BDL 77.6
124 S004 Bullet pocket 1 5-30 145 37.1 7.6 5.6 7.2 798 126,000 0.05 8.2 71.3 125
124 S007 Berm 0- 6 BDL 57.3 BDL 7.2 6.7 6,420 4,800 0.05 11.2 BDL 700
124 S009 Bullet pocket 0-6 BOL 53.7 2.1 10.1 6.0 13,200 13,600 0.07 6.1 BDL 1,350
124 S014 Berm backside 15-30 BDL 28.9 BDL 6.6 BDL 29.9 1,800 0.08 BDL BDL 105
124 S015 Sediment Surface BDL 34.4 BDL 6.0 BDL 35.0 648 BDL 6.7 BDL 39.6
111 S037 Crater bottom Surface BDL 97.3 31.1 34.8 9.0 276 112 0.05 37.7 BDL 2,120
111 S038 Crater wall Surface BDL 115 32.3 41.8 7.7 370 152 0.05 47.5 BDL 5,680
111 S039 Open area Surface BDL 94.8 94.6 27.7 6.8 1,560 90.6 0.06 31.3 23.4 691
111 S041 Open area Surface 22.6 164 32.5 44.4 12.8 364 70.1 0.06 55.2 BDL 976
111 S044 Crater bottom Surface BDL 92.0 73.6 25.8 5.8 322 70.1 BDL 29.5 BDL 703
111 S049 Background 1 5-30 BDL 61.0 BDL 16.3 6.8 11.0 26.0 BDL 7.9 BDL 48.6
Detection limit 8.0 0.6 0.4 0.4 6.0 1.0 10.0 0.04 4.0 20.0 0.4
value given for category C. One sample has a copper concentration higher than the 500 mg kg-I
value for copper and one sample has a zinc concentration higher than the 3,000 mg kg-1 value for
zinc given for category C. In addition, all the other samples (except for the background sample)
have concentrations of both copper and zinc that are higher than the 100 mg kg-! value for copper
and the 500 mg kg -1 value for zinc given for category B. One sample has a lead concentration
slightly higher than the 150 mg kg-! value for category B. Concentrations for all other heavy
metals are below the category B values and are usually within the normal range for soils
(Table 1). These data suggest that cadmium, and possibly copper and zinc, are the heavy metals
of concern at Range 111.
A split of the 18 samples listed in Table 5 was also analyzed using the TCLP procedure,
and the results of these analyses are given in Table 6. Review of the results for the Range 122
samples shows that all samples have concentrations for barium, cadmium, chromium, and lead
below the TCLP limits of detection listed in Table 4. TCLP limits for copper, tin, and zinc have
not been established at this time. Lead concentrations for all the Range 124 samples are much
higher than the 5.0 mg L-! TCLP limit, but all barium and chromium concentrations are below
TCLP limits. Cadmium concentrations in extracts from Range 111 samples, except for the control
sample, are all higher than the 0.5 mg L-1 TCLP limit. These data suggest that the TCLP
procedure is not leaching the total amount of heavy metals from the soil, but even so, these data
show that high concentrations of lead in the soil of Range 124 and cadmium at Range 111 pose
potential concerns.
The heavy-metal concentrations in the TCLP extracts were multiplied by a dilution factor of
about 20 to calculate the minimum concentration in the Grafenwthr soils that will yield a hazardous
TCLP concentration. The results of these calculations are shown in Table 7. Comparison of these
calculated values with the total heavy-metal concentrations determined by the ICP-AES method
indica't,:_the degree to which heavy metals are leached from these soils by the simulated acidic
rainwater used in the TCLP procedure.
The amount of cadmium extracted by the TCLP procedure is somewhat less than the
amount of barium, as shown by a lower concentration of cadmium in an individual sample in
Table 7 as compared with the concentration for the same sample in Table 5. Comparison of the
chromium, copper, lead, and zinc concentrations for individual samples in Table 5 with their
respective values in Table 7 suggests that these heavy metals respond in a manner similar to
cadmium. These results suggest that some portion of these heavy metals is bound in the soil and
TABLE 6 Heavy-Metal Concentrations in TCLP Extracts from Soils Collected at GTA during Apdl 1992
1 22 S016 Behind target 0 - 15 15.2 BDLa BDL 0.42 1.89 9.12 0.26
1 22 S017 Behind target 1 5-30 2.99 BDL BDL 0.04 0.03 8.23 0.02
122 S022 Bullet pocket 0-1 5 0.50 BDL BDI_ 0.38 1.01 1.74 0.14
122 S026 Berm 0-15 BDL BDL BDL 0.22 BDL 0.77 0.13
122 S029 Background 1 5-30 3.94 BDL BDL BDL BDL 4.67 BDL
1 22 S030 Sediment Surface 51.6 0.08 BDL 0.06 0.56 33.6 0.05
124 S003 Bullet pocket 0-1 5 18.4 0.02 BDL 1.80 222 15.8 0.69
124 S004 Bullet pocket 1 5-30 16.6 0.02 BDL 4.85 678 10.4 1.18
124 S007 Berm 0- 6 14.1 BDL BDL 4.01 361 7.78 0.73
1 24 S009 Bullet pocket 0- 6 22.0 BDL 1311 3.63 451 13.1 0.84
1 24 S014 Berm backside 1 5-30 45.2 0.06 BDL 0.44 51.2 28.7 0.43 _'._
1 24 S015 Sediment Surface 1.74 BEX. BDL 0.16 12.7 2.89 0.05
111 S037 Crater bottom Surface 49.0 1.08 0.02 0.95 0.62 35.8 48.8
111 S038 Crater wall Surface 52.5 1.29 0.02 1.27 0.75 37.1 76.2
111 S039 Open area Surface 51.6 4.00 0.02 3.87 0.75 33.1 33.1
111 S041 Open area Surface 36.4 2.54 BDL 0.73 0.13 17.8 9.68
111 S044 Crater bottom Surface 40.2 0.89 BDL 0.38 0.19 9.54 20.0
111 S049 Background 1 5-30 1.00 0.38 BDL 0.04 1311 BDL 0.08
122 S016 Behind target 0-15 304 BDLa BDL 8.42 37.7 182 5.19
122 S017 Behind target 15-30 59.8 BDL BDL 0.75 0.50 164 0.31
122 S022 Berm 0-15 9.96 BDL BDL 7.68 20.2 73.8 2.75
122 S026 Berm 0-15 BDL BDL BDL 4.46 BDL 15.3 2.60
122 S029 Background 15-30 78.8 BDL BDL BDL BDL 93.3 BDL
122 S030 Sediment Surface 1,032 1.61 BDL 1.20 11.2 671 1.04
124 S003 Bullet pocket 0-15 607 0.38 BDL 35.9 4,440 316 13.7
124 S004 Bullet pocket 1 5-30 369 0.38 BDL 96.9 13,600 209 23.6
124 S007 Berm 0-6 282 BDL BDL 80.2 7,200 156 14.7
124 S009 Bullet pocket 0-6 440 BDL BDL 72.6 9,000 262 16.8
124 S014 B_rm backside 15-30 904 1.25 BDL 8.76 1,000 574 8.57
1 24 S015 Sediment Surface 34.9 BDL BDL 3.22 254 57.8 1.07
111 S037 Crater bottom Surface 980 21.7 0.43 18.9 12.4 716 976
111 S038 Crater wall Surface 1,050 25.7 0.43 25.4 15.0 742 1,523
111 S039 Open area Surface 1,032 80.0 0.43 73.4 15.0 662 662
111 S041 Open area Surface 728 50.8 BDL 14.6 2.51 356 193
111 S044 Crater bottom Surface 804 17.3 BDL 7.68 3.77 191 400
111 S049 Background 15-30 19.9 0.38 BDL 0.75 BDL BDL 1.68
also that concentrations of these heavy metals in runoff waters are lower than their concentrations
in the range soils. However, if the concentration of one of these heavy metals in the soil is well
above the soil regulatory limit, this heavy metal could be transported from the range in runoff
Analytical results from the April 1992 collection of soil samples show that concentrations
of heavy metals at Range 122 are below the Dutch List category B limits and the TCLP limits
established by the EPA. These results suggest that heavy-metal contamination at Range 122 may
not be a major concern. However, the lead concentration in the sediment sample is above the
category B value, which suggests potential off-range contamination. The extremely high levels of
lead and copper in the soils at Range 124 are a major concern. Several soil samples also had
above normal concentrations of zinc. Although the concentrations of barium and tin in the soil are
below the category B value, the higher proportion of these metals measured by the TCLP
procedure than by the ICP-AES method suggests that these metals may be transported off the range
in runoff waters. The major concerns at Range 111 are the high concentrations of cadmium and
the above-normal levels of copper and zinc. In addition, potentially high levels of barium and tin
may be present in runoff waters from Range 111, because a high proportion of these heavy metals
is extracted from the soil by the TCLP procedure.
5.1.2 Explosives
Selected samples collected during April 1992 from the three ranges were analyzed at ANL
for TNT, RDX, and their explosive by-products. The potential for finding both TNT and RDX
residues at Range 111 was high because both explosives are major components in hand grenades.
Explosive residues were not expected at either Range 122 or Range 124 because these types of
explosives are not components in most small-arms ammunition. No explosives were detected
above the 1 mg kg-1 detection limit in any of the samples from any of the ranges.
A major activity during the July 1992 primary data and sample collection effort was the
collection of XRF readings at all three ranges. This activity was not included in the scope of the
original study plan, but it was added because of the potential advantages of obtaining XRF data.
Direct XRF readings can provide lead-contamination levels in soils at several locations and depths
in a relatively short time. If the method is proven by field validation, XRF data can be used to
determine lead contamination at a much lower cost than conventional soil sample collection and
laboratory analyses. A disadvantage of the XRF method is that the minimum detection limit for
lead in native soils has not been established. The XRF method has the potential to determine
concentrations of other metals besides lead. In this study, however, the resolution of the portable
XRF unit was too low to identify other metals.
The 167 individual XRF readings for lead levels taken at Range 122, including the three
replicate readings made at five locations, are listed in Table 8. Of the 157 different locations and
depths where readings were taken, samples from 129 (82%) were below the 150 mgkg "l
category B value for lead in the Dutch List. Readings for 17 locations (11%) were between the
category B value and 600 mg kg -1, the category C lead value. Only 11 (7%) readings were
higher than the category C value.
Background-level readings at Range 122 were observed between targets (transect 2) and
behind the eighth row of targets (transect 3) in the open area of the range. XRF readings between
the category B and category C lead values were recorded behind the targets, next to the trench,
and on the trench walls. The maximum depth at which any readings above the category B value
were found was at 16 era, suggesting that the interior of the berm is not contaminated with lead.
The highest levels of lead contamination were observed behind targets (transect 1) and on the face
of the berm (transect 4). Of the 11 readings higher than the category C value, only two were
from below the soil surface, at a maximum depth of 13 cm. The XRF readings taken at
Range 122 show lead contamination is limited to the surface soil.
The 222 individual XRF readings taken at Range 124, including the replicate readings at
seven locations, are listed in Table 9. Distribution of the magnitude of the readings from the
210 different locations and depths is as follows: 57 (27%) were below the category B value for
lead, 20 (10%) were between category B and category C values, and the remaining 133 (63%)
were higher than the category C value.
The lead-concentration pattern at Range 124 was not as well-defined as the pattern at
Range 122. Generally, the only areas with surface-soil readings at background levels (lower than
150 mg kg-1 lead) were behind the firing pads (transect 5 and background locations). Other
background-level readings were recorded at depths 5-15 cm below the soil surface between the
firing pads and the berm. Readings higher than 150 mg kg-1 (the category B limit) were
recorded on the soil surface throughout the range, on the berm, and on the trench walls.
The highest XRF readings recorded at Range 124 were on the berm face (transects 1, 2,
and 7) and on the trench walls. Readings in the 3,000-7,000 mg kg-1 lead range were recorded
on the trench wall to a depth of 75 cm below the soil surface. This depth of lead contamination on
the trench walls was not observed at Range 122. The reasons for the difference between the
degree of lead contami_lation at the two ranges were learned in discussions with Army personnel at
GTA. The _gh-velocity rifle slugs disintegrate into small particles on impact, while the lower-
velocity handgun slugs remain intact. Disintegration of the rifle slugs produced small lead particles
that were easily incorporated into the soil surface, while the intact handgun slugs ricocheted off the
soil surface. Thus, intact slugs were present at the handgun range (Range 122), but they were
absent at the rifle range (Range 124). Impact from the high-velocity rifle slugs also produced a
hole or bullet pocket behind the single fixed target on the face of the berm at Range 124, while
bullet pockets do not develop behind the pop up targets at Range 122. At Range 124, the face of
the berm is periodically graded, ond soil is added to fill the bullet pockets. This grading has
TABLE 8 X-Ray Fluorescence Readings Taken at Range 122 at GTA during July
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (rag kg"1) Notes
TABLE 8 (Cont.)
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (rag kg"1) Notes
2 1 0 1 0
2 5 0 1 0
2 10 0 1 0
2 15 0 1 6
2 15 0 2 64
2 15 0 3 6
2 15 7 1 0
2 20 0 1 81
2 20 7 1 0
2 25 0 1 0
2 30 0 1 0
2 35 0 1 0
2 39 0 1 0
2 44.5 0 1 0 Bottom of ditch
2 49 0 1 0
2 55 0 1 1,408 Next to trench
2 55 15 1 250 Trench wall
2 55 30 1 0
2 56 0 1 0 Next to trench
2 56 15 1 203 Trench wall
2 56 30 1 0
2 57 0 1 0 Next to trench
2 57 15 1 0 Trench wall
2 58 0 1 0 Next to trench
2 58 15 1 0 Trench wall
2 59 0 1 0 Next to trench
2 59 15 1 0 Trench wall
2 59 30 1 0
2 60 0 1 0 Next to trench
2 60 15 1 306 Trench wall
2 61 0 1 0 Next to trench
2 61 15 1 0 Trench wall
2 63 0 1 0 Top of berm
2 65 0 1 0 Backside of berm
2 67 0 1 0 Backside of berm
2 71 0 1 0 Backside of berm at base
3 0 0 1 0 Edge of range
3 5 0 1 0 In line with firing point 1
3 7.6 0 1 0
3 10 0 1 0
3 15 0 1 0
3 20 0 1 0 In line with firing point 2
3 25 0 1 0
3 31 0 1 0
TABLE 8 (Cont.)
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (rag kg"1) Notes
3 33 0 1 0
3 35 0 1 0 In line with firing point 3
3 40 0 1 0
3 45 0 1 0 In line with firing point 4
3 48 0 1 0
3 50 0 1 0
3 55 0 1 0
3 61 0 1 0 In line with firing point 5
3 63 0 1 0 In line with target
3 63 7 1 0
3 66 0 1 0
3 71 0 1 0
3 76 0 1 0 In line with firing point 6
3 78.5 0 1 0 In line with target
3 81 0 1 0
3 85 0 1 0
3 93.4 0 1 0 In line with firing point 7
3 95.5 0 1 0 In line with target
3 100 0 1 0
3 105 0 1 0
3 110 0 1 489 In line with firing point 8
3 110 9 1 0
3 125 0 1 0 In line with firing point 9
3 130 0 1 0
3 135 0 1 0
3 140 0 1 0 In line with firing point 10
3 145 0 1 0 Edge of range
4 0 0 1 0 Edge of range
4 5 0 1 31 In line with firing point 1
4 10 0 1 0 In line with target
4 15 0 1 47
4 20 0 1 734 In line with firing point 2
4 20 13 1 35
4 25 0 1 0
4 30 0 1 0
4 35 0 1 646 In line with firing point 3
4 35 12 1 9
4 35 12 2 7
4 35 12 3 16
4 40 0 1 0
4 45 0 1 0 In line with firing point 4
TABLE 8 (Cont.)
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (rag kg-1) Notes
TABLE 9 X-Ray Fluorescence Readings Taken at Range 124 at GTA during July 1992
Location" Depth Replicate Readingb
Transect (m) (cm) Number (rag kg-1) Notes
TABLE 9 (Cont.)
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (mg kg"1) Notes
1 36 45 1 7,732
1 36 60 1 3,005
1 36 75 1 2,375
1 36 90 1 0
1 37 0 1 5,688 Next to trench
1 37 15 1 2,191 Trench wall
1 37 30 1 5,271
1 37 45 1 1,957
1 37 60 1 0
1 38 0 1 4,314 Top of berm
1 39 0 1 2,443 Top of berm
1 39 15 1 6,822
1 41 0 1 2,759 Top of berm
1 43 0 1 1,028 Backside of berm
1 45 0 1 1,065 At the base of the backside of the berm
1 51 0 1 2,235 Behind berm
1 53.5 0 1 745 Behind berm
1 53.5 18 1 0
TABLE 9 (Cont.)
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (rag kg"1) Notes
4 0 0 1 0 Edge of range
4 2 0 1 0
4 4 0 1 0
4 6 0 1 430 1.5 m in front of firing pad 1
4 8.5 0 1 0
4 11 0 1 497 1.5 m in front of firing pad 2
4 14 0 1 31
4 16.5 0 1 1,796 1.5 m in front of firing pad 3
4 19 0 1 399
4 21.5 0 1 462 1.5 m in front of firing pad 4
4 24 0 1 89
4 29 0 1 299
4 31 0 1 2,092 1.5 m in front of firing pad 6
4 31 3 1 0
4 36.5 0 1 1,718 1.5 m in front of firing pad 7
4 36.5 0 2 1,720
4 36.5 0 3 1,827
4 39 0 1 214
4 41.6 0 1 1,017 1.5 m in front of firing pad 8
4 41.6 2 1 849
4 41.6 5 1 0
4 44 0 1 334
TABLE 9 (Cont.)
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (mg kg"1) Notes
TABLE 9 (Cont.)
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (mg kg"1) Notes
TABLE 9 (Cont.)
a Depth Replicate Readingb
Transect (m) (cm) Number (rag kg"1) Notes
c Bkg = backgroundsample.
resulted in mixing the small lead particles and the lead-contaminated soil into the berm during the
15 years that Range 124 has been used for target practice. The use of high-velocity ammunition
also may account for the high surface readings and low subsurface readings at Range 124.
The 66 individual XRF readings taken at Range I I l, including the replicate readings
made at four locations, are listed in Table 10. Distribution of the magnitude of the readings from
the 62 different locations and depths is as follows: 60 (97%) were at background level, 2 (3%)
were between category B and category C values, and no readings were higher than 600 mg kg-I
(category C value). Because only two values were above background levels, no defined lead
contamination pattern can be established at Range 111.
One objective of this investigation was to assess the degree of heavy-metal contamination in
the soils of the three ranges sampled at GTA. Analytical results from the initial soil samples
(collected in April 1992) showed that lead and several other heavy metals are present in above-
normal concentrations on all three ranges (Table 5). In July 1992, the primary samples were
collected from selected areas of each of the three ranges and analyzed using both the ICP-AES and
TCLP methods to provide data on the degree of heavy-metal contamination. Results of the
ICP-AES analyses are given in Table 11, and results of the TCLP analyses are shown in
Table 12.
ICP-AES analytical results from Range 122 samples are similar to the analytical results of
the initial Range 122 soil samples listed in Table 5. Except for copper and lead, concentrations of
the heavy metals are lower than their respective Dutch List category B values. Several samples
from the berm face (transect 4) have lead levels greater than 600 mg kg -1 and copper
concentrations higher than 500 mg kg -1, the category C values. Several other samples have both
lead and copper concentrations between the category B and category C values. These above-
normal levels of lead and copper were not unexpected, because some handgun ammunition used at
this range consists of copper-jacketed lead slugs, and many slugs of this type were observed on the
soil surface at Range 122. The TCLP data for Range 122 samples (Table 12) show that
concentrations of heavy metals, except for lead, are below the TCLP limits (Table 4) and confirm
the results of the initial TCLP results listed in Table 6. The two berm samples with lead levels
above the 5-mg L-1 TCLP limit also had high ICP-AES values.
ICP-AES and TCLP data and the XRF readings for Range 122 show elevated lead levels
in samples at some surface locations. Analytical results from both the initial and the primary
sample collections show elevated levels of copper in the same samples, but other heavy-metal
concentrations are within the normal range for soil. The XRF readings show that the lead
TABLE 10 X-Ray Fluorescence Readings Taken at Range 111 at GTA during July
1992 i
Locationa Depth Replicate Readingb
Transect (m) (cm) Number (mg kg"1) Notes
3 0 10 1 0 Top of berm
3 5 0 1 6
3 10 0 1 0
3 10 15 1 0
3 15 0 1 0
3 15 0 2 0
3 25 0 1 80
3 25 0 2 107
3 25 15 1 0
3 30 0 1 0
3 35 0 1 51
3 40 0 1 0
3 45 0 1 0
3 50 0 1 21
3 50 0 2 0
3 55 0 1 0
3 60 0 1 145
3 65 0 1 0
3 73.5 0 1 0 Top of berm
TABLE 10 (Cont.)
Location" Depth Replicate Readingb
Transect (m) (cm) Number (rag kg"1) Notes
4 0 10 1 0 Top of berm
4 5 0 1 0
4 10 0 1 50
4 15 0 1 0
4 20 0 1 0
4 20 15 1 0
4 25 0 1 65
4 30 0 1 0 Top of ridge through open area
4 36 0 1 0
4 40 0 1 0
4 40 10 1 0
4 45 0 1 0
4 45 0 2 0
4 55 0 1 0
4 60 0 1 0
4 65 0 1 8
4 70 0 1 0
4 75 0 1 0 Top of berm
c Bkg = backgroundsample.
TABLE 11 Heavy-Metal Concentrations Determined by the ICP-AES Method for Soils Collected at GTA during July 1992
122 1 1 0 BDLb 102 BDL 8.4 BDL 152 171 6.8 BDL 66.8
122 1 59 15 BDL 67.5 BDL 10.0 BDt. 104 384 5.9 BDL 36.8
122 Bkgc ! -16.5 0 BDL 77.2 _ 6.0 BDL 16.7 31.2 3.5 EE)L 19.1
122 Bkg 1 -16.5 30 BDL 70.5 BDL 6.1 BDL 17.5 35.9 4.4 BDL 21.6 oo
124 7 36 15 BDL 46.1 1.1 7.9 BElL 5,460 10,400 8.4 BDL 574
124 Bkg 1 -20 0 BDL 56.2 BDL 19.4 7.9 20.5 235 20.3 BDL 60.1
124 Bkg 1 -20 45 BDL 48.5 BDL 11.1 B[X. 7.4 100 7.6 BDL 32.9
TABLE 11 (Cont.)
111 1 25 0 46.7 108 27.5 SPOL d SPOt. 248 123 53.3 24.2 1,830
111 1 49 0 BDLb 73.1 6.0 22.3 BDL 65.8 81.2 25.0 BDL 2,070
111 2 25 0 31.5 82.1 131 SPOL SPOt. 633 108 36.0 30.4 566
111 3 25 0 57.1 102 46.0 SPOL SPOt. 331 142 53.8 67.7 1,990
111 3 35 0 61.5 92.7 144 SPOL SPOt. 417 143 48.6 33.1 1,110
111 3 50 0 49.4 106 36.1 SP(X. SPOt. 324 138 55.2 25.4 1,680 ¢_
111 4 45 0 45.5 99.8 128 SPOt. SPOL 566 123 38.2 21.6 650
111 Bkg 1 -20 13 BDL 27.0 BDL 6.8 BDL 1.6 BDL 6.0 BDL 24.2
111 Bkg 2 78 12 23.4 29.1 BOL SRDL SPOL 5.6 27.4 6.3 BDL 30.5
111 Bkg 3 -30 8 BDL 20.5 BDL 8.1 BDL 4.0 29.4 5.3 BDL 25.1
111 Bkg 4 92 10 BDL 19.9 BDL 5.3 1311 8.2 25.0 4.0 BDL 28.2
TABLE 11 (Cont.)
Detection limit 8.0 0.6 0.4 0.4 6.0 1.0 10.0 4.0 20.0 0.4
TABLE 12 Heavy-Metal Concentrations Determined by the TCLP Method for Soils Collected at
GTA during July 1992
contamination is limited to the surface soil, and most of the XRF readings that were higher than
600 mg kg -1 were on the face of the berm. These data suggest that the berm surface soil at
Range 122 has lead and possibly copper levels that exceed the regulatory limits. These data also
suggest that the lead and potential copper contamination are generally limited to the upper 15 cm of
soil at Range 122. The absence of high concentrations of lead, copper, and other heavy metals
below the soil surface suggests that heavy metals are not being leached through or to the lower
levels of the soil profile.
Data from ICP-AES and TCLP analyses and XRF readings from Range 124 show that the
soil in the berm and surface soil are contaminated with lead. Results of the ICP-AES analyses
given in Table 11 show that most of the soil samples from Range 124, including those collected
from the trench wall, have lead concentrations higher than the 600 mg kg-I Dutch List category C
value. Several of these same samples have copper levels that are also higher than the category C
value of 500 mg kg -1. Many samples with lead and copper levels lower than the category C
value have concentrations that are higher than the category B value. This result suggests that the
surface soil and the soil making up the berm is contaminated to some degree with lead and copper.
Several samples also have concentrations of arsenic, barium, and zinc that are between the
respective category C and category B values. These results are similar to the ICP-AES results
from the initial sample collection given in Table 5. TCLP analytical results from Range 124
samples listed in Table 12 show that the levels of heavy metals, except lead, are below the TCLP
limits (Table 4). This is consistent with the TCLP data from the initial sample collection that were
presented in Table 6. Heavy-metal contamination to a depth of 75 cm in the berm is probable
because of repeated soil mixing during regular berm maintenance activities. This contamination
may be due to disintegration of slugs from high-velocity ammunition. Contamination is probably
limited to the upper 15 cm of soil, because elevated levels of lead and other heavy metals were not
observed below the 15-cm depth in the open area of the range. This result suggests that heavy
metals are not being leached through or into the lower soil profile.
Review of ICP-AES analytical results from Range 111 samples (Table 11) shows that the
concentration of cadmium in a number of samples is higher than the 20 mg kg -1 Dutch List
category C value. Most of the other samples analyzed have cadmium levels higher than the
5 mg k_,-! category B value. Several samples also have arsenic levels higher than the
50 mg kg -1 category C value and copper concentrations greater than the 500 mg kg -1
category C value. Several additional samples have arsenic, copper, and zinc levels between the
category B and category C values. Unlike the other two ranges, Range 111 had only two
samples with lead levels higher than the 150 mg kg -1 category B value. These analytical results
are similar to the analytical results for the initial samples given in Table 5, except that arsenic is
present in elevated concentrations in the primary (July) collection. The TCLP results for samples
from Range I 11 (Table 12) show that cadmium is present at higher than the 0.5 mg L -1 TCLP
limit (Table 4) in five samples. These results are ;imilar to results from the initial TCLP sample
analyses listed in Table 6. The high TCLP values show that a portion of the cadmium at such high
soil concentrations can be leached from the soil with simulated rainwater. These data also show
that heavy metals are in both surface and subsurface samples over the open area of Range 11I.
Analytical results for the vegetation samples collected from the three ranges at GTA are
shown in Table 13. Comparison of these values with the normal concentration of heavy metals
found in plant leaves (Table 1) shows that the chromium, copper, and zinc concentrations are all
within the normal range. Tin levels in the vegetation probably do not pose a problem, because all
vegetation samples are below the detection limit. However, an assessment cannot be made because
published information is not available on the normal concentration of tin in plants.
A few samples from each of the three ranges show barium levels higher than the expected
normal range of 10-100 mg kg-1 in plant leaves. These higher levels may be due to the higher
proportion of barium in the soil solution, as suggested by the higher proportion of barium
compared with other heavy metals extracted by the TCLP procedure (Table 7). These levels of
barium are not considered a concern, because they are only slightly above the normal range in plant
One-half of the vegetation samples collected at Range 111 have cadmium levels above the
normal range of 0.05-0.2 mg kg -1 in plant leaves. These elevated levels of cadmium are
consistent with the elevated cadmium levels in the soil at this range. The above-normal levels of
cadmium could be from plant uptake or from external contamination from soils.
The intake of lead and cadmium by wildlife is probably not a major concern, because the
relatively small amount of vegetation contaminated by these heavy metals and available to wildlife
as food is limited. There is abundant uncontaminated vegetation around all the ranges. The intake
of contaminated plant material as food is probably only a small portion of the total diet of area
Analytical results of the surface water collected at Ranges 122 and 111 are listed in
Table 14. Evaluation of the chromium and lead data with regard to the suggested maximum
concentration in drinking water is not possible because the detection limits for these heavy metals
are higher than the suggested maximum concentration in drinking water (Table 3). Evaluation of
the tin and zinc data is also not possible because maximum safe concentrations have not been
established at this time.
TABLE 14 Heavy-Metal Concentrations in Surface Water Collected at GTA during July 1992
122 4 North end of berm 1.10 0.03 BDLb BDL BDL BDL 0.19
111 1 32 m south, 0 m east 2.30 0.04 BDL BDL BDL BDL 0.12
111 2 10 m south, 10 m east 3.70 0.04 BDL. BDL BDL BDL. BDL
111 3 40 m west, 4 m north 2.20 0.05 BDL BDL BDL BDL BDL
111 4 36 m west, 1 m north 3.80 0.04 BDL BDL BDL BDL BDL
111 4 50 m west, 7 m north 3.00 BDL BDL BDL BDL BDL 0.16
111 4 44 m west, 0 m north 3.70 0.05 BDL BDL BDL BDL BDL
Inspection of the analytical data from the surface water at both ranges shows that
concentrations of barium and cadmium in all samples exceed the suggested maximum drinking-
water concentrations of 0.05 mg L -1 for barium and 0.005 mg L -1 for cadmium. These results
may be due to the extractability of barium and the high concentration of cadmium in the soil at
Range 111, but there is no apparent reason for the elevated level of cadmium in the water sample
from Range 122.
Potential saving of both time and cost can be realized by using the XRF method to measure
lead and other heavy-metal contamination at firing ranges. The unit used in this investigation was
calibrated by the manufacturer for lead in soil. However, the minimum lead detection limit under
field conditions and the variation of XRF lead values over a range of concentrations was not
available before this investigation. The comparison of XRF and laboratory analytical data
discussed below was undertaken to assess the usefulness of the XRF method in future
investigations of this type.
Precision and accuracy are two measures of the quality of analytical data produced by a
given method. To provide an estimate of the quality of XRF field measurements, two 750-g
samples of soil were collected from Range 124. One sample (No. 1) represented soil with an
intermediate XRF lead reading, while the second sample (No. 2) represented soil having a high
XRF reading. These samples were air-dried and homogenized, and eight replicate XRF readings
were taken. At ANL, four replicates from each sample were analyzed for lead by the ICP-AES
method. The field XRF lead readings and corresponding ICP-AES lead values for the two
samples from Range 124 are listed in Table 15.
The accuracy of the XRF method is dependent on the concentration of lead in the soil. The
percent relative standard deviation for the XRF readings from sample 1 is about 8%, and for
sample 2, approximately 10%, which is a very acceptable level of precision for a field method.
One ICP-AES outlier value in each sample may indicate the heterogeneity of fine lead particles in
the soil that could result from the uneven distribution of lead particles during the disintegration of
the slug on impact. For sample 1, the field XRF mean of 1,200 mg kg -1 and the ICP-AES mean
of 1,400 mg kg -1 agree satisfactorily if one ICP-AES outlier data point is excluded from the
calculation. For sample 2, with a somewhat high lead level, the XRF mean of 5,050 mg kg -1 is
substantially lower than the ICP-AES mean of 8,930 mg kg-1, again with one ICP-AES outlier
omitted. The XRF readings are expected to be biased toward lower readings on samples with high
TABLE 15 XRF Lead Readings and Corresponding ICP-AES Lead Values for Two Soil
Samples Collected from Range 124 at GTA during July 1992
Sample1 Sample2
lead concentrations because the number of fluoresced X-rays absorbed by the lead in the sample
increases as the concentration of lead in the sample increases.
The XRF readings at 51 locations in the field were compared with the lead concentrations
at the same locations as determined by laboratory ICP-AES analysis (Table 11). Of the 51 pairs,
27 had XRF readings of 0 mg kg -1 compared with a mean lead concentration of 93.7 mg kg-1 by
the ICP-AES method. Of the data pairs with XRF readings of 0 mg kg -1, the lowest
corresponding ICP-AES lead concentration was 50 mg kg-1 and the highest was 366 mg kg-1
lead. These results suggest that the limit of detection of the portable XRF unit used in this study
for the field conditions at GTA was between about 50 and 400 mg kg-l. This limit of detection
was acceptable for measuring lead concentration in this study, because it is below the
600 mg kg -1 Dutch List category C lead value. However, a lower limit of detection would be
For the 12 samples having XRF readings between 0 and 600 mg kg -1 lead, only two
samples had ICP-AES lead concentrations lower than their XRF readings. Of the ten remaining
samples in this XRF range, two had ICP-AES lead values higher than 600 mg kg -1 lead. Of the
12 samples with XRF readings higher than 600 mg kg-1, only three had XRF readings higher
than their ICP-AES values. The underestimation of lead concentration in this range of XRF
readings is expected and is caused by the bias toward lower XRF readings on samples with high
lead concentrations. Of the 24 samples having XRF readings higher than 0 mg kg-1, the XRF
readings are within 50% of the XRF reading for only eight samples.
This variation in the degree of agreement between the XRF and ICP-AES results may be
due to the nature of the lead contamination. As previously discussed, lead contamination on small-
arms ranges usually consists of fine metallic particles that are very heterogeneous in the soil. The
somewhat small area exposed for the XRF reading may not be identical to the one gram taken for
the ICP-AES analysis. Better correlation between the XRF and ICP-AES results would be
required for the field XRF method to be useful as more than a screening tool.
The XRF unit used in this study produced a spectrum of X-rays emitted during each
reading, as previously discussed in Section 4.3.2. Each spectrum was copied to a computer and
printed later for inspection. On a printed spectrum (Figure 9), the x-axis represents the X-ray
energy levels (channels) emitted by the sample, and the y-axis represents the number of X-rays
(counts) for an energy level. The first 25 channels of the spectrum are used for identification and
other related information and do not represent X-ray energies from the sample. The first peak, up
to channel 35, is from the 109Cd source. The larger peak to the right, at about channels 150 to
160, is the Compton backscatter peak caused by backscatter from the 109Cd gamma ray source.
The lead L-shell emission peaks are at about channels 80 to 100. An algorithm that uses the
o 1500
L-shell emissions and the Compto_! backscatter is used to identify and quantify lead in the sample.
Bands of channels with emissions from chromium, copper, nickel, and zinc appear between the
109Cd peaks and the lead peaks.
The printed spectra of three XRF readings collected from Range 124 at GTA during July
1992 are shown in Figures 9-11. The readings are compared in Table 16 with the heavy-metal
concentrations for samples collected at these locations and analyzed by the ICP-AES method.
Theoretically, concentrations of heavy metals other than lead can be determined by inspection of
the spectrum. In Figures 9-11, it is difficult to distinguish the peaks and, thus, determine the
concentration of lead because of the low resolution of the printed spectrum. This poor resolution
makes it impossible to identify the peaks and concentrations of chromium, copper, nickel, and
zinc. Due to these limitations, inspection and review of individual spectra were not pursued.
Another objective of this investigation was to relate the general soil, geologic, and
geochemical conditions at the ranges to the mobility of heavy metals. The physical and chemical
characteristics of the soil are important factors influencing the mobility of heavy metals. The
analytical results for selected parameters of soil samples collected at the training ranges are shown
in Table 17.
0 _H_H_H_H_mH_H_H_H_B_B_H_H_H_B_HBW_H_"_BH_BHBB_B
FIGURE 10 XRF Spectrum 2: Sample with 1,796 mg kg-1 Lead Collected from Range 124 at
GTA during July 1992
, =
FIGURE 11 XRF Spectrum 3: Sample with 4,569 mg kg "1 Lead Collected from Range 124 at GTA
during July 1992
XRFReading ICP-AESMethod
Number Pb Cr Cu Pb Ni Zn
Soil reaction or pH is one factor that influences the availability of most heavy metals in
soils. Generally, as soil pH increases, the availability of heavy metals decreases, because more
cations are bound to the clay and organic matter in the soil. Liming the soil to raise the pH is a
technique used sometimes to reduce the availability of heavy metals in soils. A review of the pH
values in Table 17 shows that the soils at Ranges 124 and 111 are slightly alkaline. This
alkalinity could moderately reduce the availability of heavy metals at these ranges. The soil at
Range 122 is slightly acidic, so the availability of heavy metals may be slightly higher as
compared with the other two ranges. Considering the above-normal concentrations of some of the
heavy metals in the soils at all three ranges, soil pH is probably not a major factor influencing the
availability of heavy metals in these soils.
The percentage of carbon in a soil is an indirect measurement of the organic matter content.
The amount of organic matter and the type and amount of clay influence the cation exchange
capacity (CEC) of a soil. This capacity is reflected by the two soil samples having about 2%
carbon that also have much higher CEC values than the t)ther samples. The amount and type of
clay in soils also influence the CEC. Generally, soils with low proportions of clay, such as the
GTA soils, have a lower CEC than soils with more clay. Differences in CEC due to the clay
content of the GTA soils are not obvious, because of the minor differences in the clay content.
Cations, including heavy metals, are more easily leached from soils with a low CEC than from
soils with higher CEC. This finding would suggest that heavy metals could be leached from the
GTA soils because of their somewhat low CEC. However, this is also probably a minor factor in
the transport of heavy metals from the ranges into the local environment.
Another factor influencing the leaching of heavy metals through the soil profile is soil
texture. Coarse-textured soils (sands, loamy sands, and sandy loams) generally have higher water
infiltration rates than fine-textured soils (clay, silty clay, and sandy clay). Because of the coarse
texture of GTA soils, a high proportion of the rainwater falling on a training range will infiltrate the
soil and leach heavy metals lower into the soil profile. However, a finer textured soil will allow a
higher proportion of runoff, carrying heavy metals and sediment into adjacent areas.
TABLE 17 Physical and Chemical Characteristics of Soils Collected at GTA during July 1992
The physical and chemical characteristics of soils and geochemical factors are important
influences on the mobility of heavy metals in the environment. As part of a concurrent study using
the soil samples from GTA to determine the amount of heavy metals leached from the soil by
various media and methods, soil columns were flushed five times with an amount of distilled water
equal to the pore volume. Preliminary results from this experiment show that less than 4% of the
total cadmium content and even smaller amounts of other heavy metals were removed (Peters
1993). This and other column flooding experiments suggest that the heavy metals are not easily
leached from the GTA soils.
There is additional evidence that heavy metals are not easily leached into the soil profiles at
the three training ranges examined in this study. Both the XRF readings and the analytical data
show that lead and other heavy metals are normally limited to the upper 15 cm of the soil surface.
High levels of heavy metals in samples from the trench walls were caused by range maintenance
activities, not by leaching. Results of our study show that heavy metals are not contaminating the
lower portions of the soil profile.
Another objective of this study was to estimate the geographic extent of local and off-site
heavy-metal contamination. A potential method for transporting heavy metals into the adjacent
environment is by runoff of water and sediment. The areas around all three ranges are relatively
level, so runoff sediment moving out of GTA is not a potential problem. There is some indication
that runoff water, carrying sediments, does leave both Ranges 122 and 124 via the drainage ditch
in front of the berm. Analytical results from sediments collected in April 1992 suggest sediments
contain elevated levels of some heavy metals. Some areas within the local drainage system could
have heavy-metal contamination due to sediment accumulation. There is no evidence of surface-
water runoff from Range 111, and it is unlikely there is heavy-metal contamination in adjacent
areas caused by sediment accumulation.
Results of ICP-AES analyses indicate that most soil samples from Range 122 (handgun
range) have lead concentrations that are above the Dutch List category B level (150 mg kg-l), and
several samples are above the category C level (600 mg kg-1). Copper concentrations in some of
these soil samples also are above the category B level (100 mg kg-l), but they are below the
category C level (500 mg kg-l). Concentrations of other heavy metals in soil samples from
Range 122 are within their normal ranges. Analytical results of TCLP extraction of soil samples
show that lead can be leached from soils in concentrations (>5 mg L-1) that would cause this soil
to be classified as hazardous waste. Soil-sample analytical data and XRF readings show that lead
contamination at Range 122 is limited to the surface soil of the berm and the areas directly behind
Analytical results from vegetation samples collected at Range 122 show above-normal lead
levels. The source of the lead could be high levels in the soil being taken up by the plants or
external contamination by lead particles and soil. In either case, vegetation being consumed by
wildlife contains elevated lead levels. The amount of potentially contaminated plant material on the
ranges is small compared with the total vegetation in the area. Consequently, the overall concern
for elevated lead levels in wildlife diets is minor. The water sample from Range 122 has barium
and cadmium levels above the suggested maximum concentrations in drinking water, and a
sediment sample from Range 122 has an above-normal concentration of lead, suggesting that lead
may be transported from the range along with runoff waters into adjacent drainage ways. The
physical and chemical characteristics of the soil at Range 122 suggest that heavy metals are not
tightly bound in the soils. Analyses of the soil show that heavy metals are not being leached
deeper into the soil profile. Analytical data for the groundwater from a well in the area show that
heavy metals are not above the normal concentrations. Range 122 has the lowest heavy-metal
contamination of the three ranges included in this study.
ICP-AES results from soil samples collected at Range 124 (rifle range) show that lead and
copper concentrations are above the Dutch List category C levels (600 mg kg-1 and 500 mg kg -1,
respectively). These results also indicate concentrations above the Dutch List category B levels for
arsenic (30 mg kg-1), barium (400 mg kg-1), tin (50 mg kg-l), and zinc (500 mg kg -1) in
some soil samples. The elevated levels of lead and copper are genuine, because a number of soil
samples have consistently high concentrations of these two heavy metals. The arsenic, barium,
tin, and zinc levels may be suspect because they occur in only a few samples and are only slightly
over normal concentrations. Analyses of TCLP extraction of soil samples indicate that lead is
leached from contaminated soils at levels (>5 mg L-1) that would cause these soils to be classified
as hazardous waste. Soil analytical data and XRF readings show that the soil surface and the
interior of the berm are highly contaminated with lead and possibly with copper. This
contamination is produced by the type of weapons fired at this range and by regular berm
maintenance activities. These data also show that soils below the 15-20 cm depth on the open area
of the range do not contain above-normal concentrations of heavy metals.
Results of the vegetation analysis indicated above-normal concentrations of lead and barium
in plants at Range 124. The elevated concentrations may be caused by uptake from high lead and
barium levels in the soil or by external contamination of the vegetation. Because of the possibility
of introducing contaminated plant materials into local food webs, the above-normal concentrations
could be a concern. Only a relatively small amount of vegetation, as compared with the total
vegetation available in the area, may be contaminated, so these elevated levels probably do not pose
a threat to wildlife. Data indicate a high lead level in the sediment at Range 124, with the
possibility of lead being transported by runoff into the adjacent drainage ways along with
sediments. Surface water from this range was not available for analysis. Physical and chemical
properties of soil at Range 124 were similar to those at Range 122, suggesting that heavy metals
are not tightly bound in these soils. However, there is no evidence that heavy metals are being
leached into the lower portions of the soil profile at Range 124, nor is there evidence that
groundwater in the area is being contaminated by heavy metals from Range 124. Of the three
ranges investigated in this study, Range 124 has the highest lead contamination, as well as
possible copper contaminat,_on.
Results from analyses of soil samples from Range 111 (hand-grenade range) by the
ICP-AES method indicate that concentrations of arsenic (50 mg kg-1), cadmium (20 mg kg'l),
and copper (500 mg kg-1) are above the Dutch List category C levels. Zinc concentrations are
also above the category B level (500 mg kg-I) in many soil samples. Concentrations of other
heavy metals are generally within the normal range for soils. Results from analyses of TCLP
extractions indicate that cadmium is leached from contaminated soils at levels (>0.5 mg L -1) that
would cause these soils to be classified as hazardous waste. Analyses for explosives show that
residues of TNT and RDX are not present at Range 111.
Vegetation samples from Range 111 show the presence of above-normal concentrations of
cadmium and arsenic. The elevated level of cadmium could be a potential concern with respect to
wildlife, but the amount of contaminated plant material is small compared with the total volume of
vegetation available in the area. Sediments were not available for sampling at Range 111, but
standing-water samples did have high levels of both cadmium and barium. Because of the fiat
topography of Range 111, transport of these contaminates to adjacent areas would not be
expected. The physical and chemical characteristics of the soil at Range 111 are similar to those of
the other two ranges, suggestihg that heavy metals are not tightly bound in the soils. Analysis of
groundwater from the area shows no evidence of contamination. Soil, vegetation, and surface-
water data indicate potentially hazardous levels of cadmium and possibly arsenic at Range 111.
This study also evaluated the effectiveness of a commercially available, hand-held XRF
spectrum analyzer for determining lead levels in soil at the three training ranges at GTA. XRF
readings were compared with laboratory results to evaluate the accuracy and precision of the XRF
unit. The detection limit for this unit under field conditions at GTA ranged from 50 to
400 mg kg-1 lead. This limit was acceptable because 600 mg kg -1 lead is the level of concern in
this study, but a lower detection limit is highly desirable. Agreement between XRF readings and
laboratory results was low, which may have been due to the variable distribution of fine lead
particles in the soil. Better correlation between XRF readings and laboratory results is necessary
for the XRF unit to be useful as more than a screening tool. However, the hand-held XRF unit is
a useful field screening tool for making large numbers of lead readings quickly and inexpensively.
Currently, the only apparent mode of heavy-metal transport into adjacent environments is
by runoff waters and sediments at Ranges 122 and 124. This heavy-metal transport could be
reduced by the construction of small runoff retention and sediment collection ponds, designed to
collect runoff only from the open area and berm face. It is not necessary to retain runoff from the
parking lots or from behind the firing lines, because these areas are not contaminated. A runoff
retention structure is not necessary at Range 111, because the level topography of the area
prevents runoff from occurring.
Results of this investigation show that there are elevated concentrations of some heavy
metals in the surface soil at all three ranges and in the berm soil at Range 124. The heavy metals
appear to be bound in the surface soil and are not being leached deeper into the soil profile.
However, the immediate remediation of these ranges is neither practical nor necessary at this time.
The removal of contaminated soils would accomplish little, because continued training activities
would quickly contaminate the surface of the replaced soil. Indeed, moving these contaminated
soils would transport heavy metals to other environments. At present, contamination is limited to
the surface soil, and data show that heavy metals are not being leached into the lower soil profile or
groundwater. The control of runoff waters and sediments would prevent heavy-metal
contamination in adjacent areas. Data from this study do indicate that remediation of these ranges
will be necessary at the termination of military training activities at the Grafenw6hr Training Area.
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