SPECIAL REPORT 95-25

Simple Field Screening Method for

White Phosphorus (P4) in Sediment

Marianne E. Walsh, Charles H. Racine, Charles M. Collins,

Carl Bouwkamp and Philip G. Thorne October 1995
Abstract

A simple field screening method to detect white phosphorus particles in

sediment is described. A thin layer of wet sediment is heated until all water

evaporates. The presence of white phosphorus is indicated by visual detection of the inflammation of white phosphorus particles that occurs at relatively low temperatures (less than 40°C) once a protective layer of water is

removed. The field screening method consistently gave positive results for

samples where solvent extraction followed by gas chromatography indicated white phosphorus concentrations above 1 μg/g. A more sophisticated method, based on solid-phase microextraction and gas chromotography

determination, was also tested. Concentrations less than 1 μg/kg were

detectable.

For conversion of SI units to non-SI units of measurement consult ASTM

Standard E380-93, Standard Practice for Use of the International System

of Units, published by the American Society for Testing and Materials,

1916 Race St., Philadelphia, Pa. 19103.

This report is printed on paper that contains a minimum of 50% recycled

material.
Special Report 95-25

Simple Field Screening Method for

White Phosphorus (P4) in Sediment

Marianne E. Walsh, Charles H. Racine, Charles M. Collins,

Carl Bouwkamp and Philip G. Thorne October 1995

Prepared for

U.S.ARMY ENVIRONMENTAL CENTER

SFIM-AEC-ETD-CR-95040

Approved for public release; distribution is unlimited.

US Army Corps


of Engineers

Cold Regions Research &


Engineering Laboratory
PREFACE

This report was prepared by Marianne E. Walsh, Chemical Engineer, Applied

Research Division, Charles H. Racine, Research Ecologist, Charles M. Collins,

Physical Scientist, and Philip Thorne, Physical Scientist, Geological Sciences Division, Research and Engineering Directorate, U.S. Army Cold Regions Research

and Engineering Laboratory, Hanover, New Hampshire, and Carl Bouwkamp,

Biologist, U.S. Army Environmental Hygiene Agency, Aberdeen Proving Ground,

Maryland.

Funding for this work was provided by the U. S. Army Environmental Center,

Martin Stutz, Project Monitor. Several people were involved in the field phase of

this work. The authors gratefully acknowledge Ronald Bailey, David Dillingham,

and Marilyn Racine. Beth Nadeau and Susan Taylor provided support in the

laboratory. Dr. Thomas F. Jenkins and Dr. Clarence L. Grant provided technical

review of the manuscript.

The contents of this report are not to be used for advertising or promotional

purposes. Citation of brand names does not constitute an official endorsement or

approval of the use of such commercial products.

ii
INTRODUCTION

Analytical methods have been developed for

white phosphorus (WP, P4) residues in sediment

and water (Walsh and Taylor 1993 and Walsh

1995). These methods require that a field sample

be brought to a laboratory where a subsample is

extracted with solvent and the extract analyzed

by gas chromatography. The cost of this analysis

is approximately $120 per sample. These methods have been used to analyze several thousand

samples from Eagle River Flats (ERF), the impact

area on Fort Richardson, Alaska (Racine et al.

1992, 1993) and from 24 other Army sites (Simmers et al. 1994).

WP contamination coincides with areas of numerous impact craters with standing water (Racine et al. 1993). Within these areas, high concentrations of WP are distributed in areas less than a

meter in diameter, which presumably correspond

to the point of impact of a WP projectile. Immediately surrounding the impact points are large

areas where WP is at very low concentration

(<0.001 μg/g) (Walsh and Collins 1993). Samples

with high concentrations were found to contain

WP particles ranging in size from less than 0.1 to

5 mm (Racine et al. 1993, Walsh and Collins 1993).

Since Army training areas tend to be large (several square kilometers) and WP tends to be heterogeneously distributed in discrete and relatively

small (less than 1-m2) areas, the number of samples required to screen an area for contamination

can be unrealistically large. Depending on the

objectives of a sampling effort, the costs and time

required for laboratory analyses may be unacceptable.

The objective of this work was to develop a

quick and easy, low cost method to detect millimeter-size particles of white phosphorus. The

method was designed so that many samples could

be tested for white phosphorus in the field without the use of organic solvents or sophisticated

equipment. In addition, a screening procedure

based on solid phase micro-extraction (SPME)

(Zhang and Pawliszyn 1993) was tested. This

SPME procedure, however, requires the use of a

field-portable gas chromatograph.

METHODS

Materials

White phosphorus (P4) and isooctane were obtained from Aldrich Chemical Company.

In the laboratory, white phosphorus particles

with diameters ranging from 0.3 to 1.8 mm were

produced under water from molten white phosphorus using a Gilson Microman Positive Displacement Pipet (size M25) equipped with disposable capillaries and pistons. The diameter of each

particle was measured using a SPI (Swiss Precision Instruments) 6-in. caliper with 0.1-mm gradations.

Solid phase micro-extraction fiber (100-μm

polydimethylsiloxane) assemblies were obtained

from Supelco.

Collection of

sediment samples

Sediment samples were collected from Eagle

River Flats, Ft. Richardson, Alaska, a site contaminated from white phosphorus munitions (Racine

et al. 1992, 1993). Sediment samples were collected by two methods. For the first method, a sample site was chosen, and then several small samples of the surface sediment within a 0.5-m radius

Simple Field Screening Method for

White Phosphorus (P4) In Sediment

MARIANNE E. WALSH, CHARLES H. RACINE, CHARLES M. COLLINS,

CARL BOUWKAMP AND PHILIP G. THORNE
were combined in a 500-mL jar. Each jar was filled

to capacity. The second sampling method involved

scooping several samples of sediment into a wash

bucket equipped with a no. 30-mesh (0.59-mm)

sieve and stirring the sample underwater. This

procedure preconcentrated the sample by removing most of the fine-grained silt particles. The

material left on the sieve was placed in a 500-mL

jar with enough water to cover the sample. Samples collected by either method were cooled to

4°C and stored in the dark until analyzed.

Detection of WP particles

Field method

Each sample was prepared for analysis by taking an approximately 20- to 30-mL subsample

and spreading it across the bottom of a 20-cmdiam. aluminum pie pan. The subsample was

spread in a thin layer (approx. 1 mm thick). Highly organic, fibrous samples were pulled apart.

Depending on the size of the sample and the objective of the analysis, several subsamples were

taken.

To detect WP particles, the aluminum pie pan

with a thin smear of sample was placed on a

heated surface. In the field, we used a double burner propane camp stove (American Camper propane

stove) and a cast iron pancake griddle (Wagner’s

1891 cast iron cookware) (Fig. 1a and 1b). In the

lab, we used a hot plate (Corning) set on the

highest setting. The hot plate was placed in the

back of the fume hood and the shield of the fume

hood pulled down.

The heat from the stove or hot plate evaporated the water from the sample and ignited WP

particles, if they were present. A positive test for a

WP particle was indicated by a localized area of

intense smoke and flame and the formation of a

bright orange residue (Fig. 2). The orange residue,

a mixture of oxidation products of WP (Daasch et

al. 1969), is hygroscopic and, if the residue was

surrounded by sediment, the sediment also appeared moist. The moist sediment was darker than

the light gray, dried ERF sediment, forming a

dark halo around the orange residue. The

orange residue also had a garlic-like odor, probably due to the production of P4O6.

Solid phase micro-extraction screening method

A 40-g wet sediment subsample, measured with

a field-portable balance (Ohaus model CT200),

was placed in a 120-mL jar equipped with a

septa-top. A 10-mL aliquot of reagent grade water (MilliQ, Millipore) was added and the sample

was equilibrated at room temperature for one hour.

b. A thin smear of sediment is heated until all water

evaporates.

Figure 1. Field test for the detection of white phosphorus particles in sediment.

Figure 2. Positive test for a WP particle. This consists

of a localized area of intense smoke and flame, and the

formation of a bright orange residue (dark gray in this

black-and-white picture).

a. Preparation of samples for field test.

2
The sample was shaken vigorously by hand; then

the SPME phase was exposed to the headspace

for 5 min. The SPME phase was immediately

transferred to a heated (200°C) injection port of a

portable gas chromatograph (SRI Model 8610)

equipped with a nitrogen-phosphorus detector.

The polydimethylsiloxane fused-silica column

(J&W DB-1, 15 m × 0.53 mm i.d., 3-μm film thickness) was maintained at 80°C and the carrier gas

was nitrogen set at 30 mL/min.

Laboratory method

White phosphorus concentration (μg/g) was

determined using isooctane extraction of a 40-g

wet subsample followed by gas chromatography

(Walsh and Taylor 1993).

RESULTS AND DISCUSSION

Initial tests

Initially, we collected samples from sites where,

using the laboratory method, we previously had

detected WP and from two sites where WP was

not detected (Racine et al. 1993a and b). At each

sample site, a 500-mL jar was filled with sediment

and subsamples were smeared across the bottom

of aluminum pie pans. Samples were tested for

WP by heating each pan on a camp stove.

For each sample where we had detected WP

above 1 μg/g by the laboratory method, we obtained a positive result by the field test for at least

one subsample (Table 1). Samples with lower concentrations apparently did not contain white phosphorus particles large enough to produce a visible flame or leave orange residue. Based on these

results, we concluded that the field test provided

a means to quickly detect large (millimeter size)

WP particles if they were present in the subsample taken, but several subsamples may be required

to obtain a positive result for samples with few

particles.

We then questioned how many subsamples

should be tested if the first subsample yielded a

negative result. A 500-mL jar contains sufficient

material for approximately 20 subsamples; however, testing so many subsamples per sample

would be extremely tedious. Next we tried preconcentrating what remained of samples 2–8

(Table 1) by sieving through a 30-mesh (0.59-mm)

sieve to remove most of the fine-grain silts and

clays and reduce the volume of the sample so that

only one test need be run. No more particles were

found in samples 2–6; however, four more particles were found in sample 7 and two more in

sample 8.

Composite sampling

Since sieving provides a means to reduce the

volume of a sample, we tested sieving in the field

as a means to create composite samples from a

large area (Fig. 3). Dabbling ducks at Eagle River

Flats have proved to be efficient samplers of white

phosphorus particles as evidenced by their high

mortality. We reasoned that by simulating the way ducks feed, by sieving several small sediment samples over a large

area, we might increase the efficiency of

sampling. Our concern over a sampling

method stems from the way in which the

marsh was contaminated. Projectiles containing white phosphorus produce discrete and relatively small areas of contamination. For example, following the

detonation of 81-mm mortar rounds the

areas containing the majority of the white

phosphorus residue were only 0.5 m in diameter (0.2 m2) (Walsh and Collins 1993).

To sample for such a small hot spot with

90% confidence (β = 0.10) using a grid

pattern of sampling would require a 0.9-

m grid spacing (Gilbert 1987). When we

consider that Eagle River Flats contains

700,000 m2 of ponds, the grid approach

to sampling would be unrealistically costly, even where multiple hot spots exist.

Table 1. Comparison of white phosphorus concentrations

found by laboratory method and number of white phosphorus particles detected by field method.

Number Number

WP conc. subsamples WP particles

Sample Sample ID (μg/g) tested found

1 1248 ND 2 0

2 AEHA BT1 ND 10 0

3 AEHA PB1 0.0143 10 0

4 AEHA D2 0.079 10 0

5 AEHA DUP1 0.205 10 2

6 AEHA D1 0.43 10 0

7 AEHA C2 1.6 10 1

8 240 2.32 10 1

9 53 10.2 2 1

10 1247 88 1 23

11 1245 168 2 7

12 110 590 2 2

13 AEHA PB2 1740 1 12

14 1246 3,071 1 68

15 MHB site 5600 1 >100

ND = not detected

3
a no. 30-mesh (0.59-mm) sieve and a large, longhandled stainless steel spoon to collect several sediment samples over a radius of up to 5 m or along

a transect that included two or more discrete sample sites (Fig. 3). The wash bucket was held underwater and the sample continuously stirred to

reduce the volume. Samples were taken until the

volume of material on the sieve was approximately

500 mL.

Sieved samples were tested for the presence of

WP particles by heating at least four subsamples

in the field. The test was performed by a field

technician with no prior experience using this

test. The technician was instructed to examine

each plate for orange residue (Fig. 4). Then both

sieved and discrete samples were returned to the

laboratory where a subsample was extracted with

isooctane and analyzed by gas chromatography.

Of the 17 samples taken, nine were blank by all

three analyses (Table 2). One sample (no. 12) was

reported to be positive by the field test, but not by

the laboratory method. This result may be due to

heterogeneity in the distribution of particles or by

flecks of iron in the sample that resemble the

orange burn residue left by a white phosphorus

particle. The remaining seven samples were positive by the field test and by the laboratory analyFigure 3. Composite samples collected using a large,

long-handled stainless steel spoon and wash bucket

equipped with a no. 30-mesh (0.59-mm) sieve. The

composite was made from several sediment samples over a

radius of up to 5 m or along a transect which included two

or more discrete sample sites.

To test the compositing approach to sampling,

two people took samples simultaneously in ponded areas of Eagle River Flats. The first person

chose a site and then took a 500-mL sediment

sample by combining several small samples of

the surface sediment within a 0.5-m radius. The

second person used a wash bucket equipped with

Table 2. Number of white phosphorus particles detected in sieved composite samples by the field method and WP concentration found by the laboratory method in

a separate subsample of each sieved composite.

Number of

Number of WP particles WP concentration* (μg/g)

subsamples from detected in Sieved Not sieved

Sites sieved composite sieved composite composite discrete

1 1295–1296 4 1 0.200 ND

2 1297 6 1 0.034 0.017

3 1292 4 60 603 0.03

4 1289 4 0 0.012 0.068

5 1293 4 59 923 0.34

6 1299–1300 5 2 26.0 0.42, 0.001

7 1290 4 46 1410 431

8 1301–1306 4 0 ND ND

9 1310 4 0 ND ND

10 1313 4 0 ND ND

11 1314 4 0 ND ND

12 1317 4 3 ND ND

13 1318 4 0 ND ND

14 1319 4 0 ND ND

15 1321 4 0 ND ND

16 1322 4 0 ND ND

17 1324–26 4 0 ND ND

* Determined by laboratory method.

ND = not detected

Note: Also shown are WP concentrations found in discrete samples taken from the same location as

the sieved composites.

4
sis of the sieved composite. WP concentrations in

the sieved composite, as determined by the laboratory method, were higher in six out of the seven

samples by up to four orders of magnitude than

the discrete sample (Table 2). The higher concentration was caused by preconcentration of white

phosphorus particles or by the increased likelihood of hitting a hot spot when taking samples

over a large area.

Additional composite samples were taken from

a ponded area in Eagle River Flats that had been

intensively sampled in the past and where many

ducks were observed to die of white phosphorus

poisoning. The area was divided into six 7.5- m ×

20-m blocks and 25 samples were collected from

each block (Fig. 5). These samples were mixed

together and sieved to produce a single sample

for each block. Each composited sample was tested using the field method by dividing into several pans and heating. (One drawback of sieving is

that it also concentrates organic matter that makes

it difficult to spread the sample across a pie

plate in a thin layer.) After removing as much

material as possible from each sample jar for the

field tests, 10.0 mL of isooctane was added to

each jar to rinse the sides and the rinsate analyzed

by gas chromatography.

White phosphorus particles were detected in

two of the six areas, four in block 5 and one in

block 2. The diameters of the orange spots produced during these tests were measured, ranging

from 1.7 to 3.4 mm for the sample from block 5

and 4.9 mm for the sample from block 2. WP was

also detectable in the rinsate from the block 5 and

block 2 jars and not in the rinsate from the other

jars. Block 5 was the only area where a WP concentration above 1 μg/g was detected previously.

Estimation of

WP particle size distribution

This field technique is not quantitative, but it

may yield some information on the WP particle

size distribution in a subsample. While testing

sediment samples using the field method, we noticed that the diameter of the orange residue varied from a fraction of a millimeter to over a centimeter. To see if there was a relationship between

the size of a WP particle and the diameter of burn

residue, in the laboratory we produced spherical

WP particles ranging in diameter from 0.3 to 1.8

mm and placed the particles in a smear of wet

sediment in an aluminum pie pan. We then heated the sample until the water evaporated and the

WP particles ignited. We measured the diameter

of the orange residue produced, and found good

correlation (r

2 = 0.903) (Fig. 6) between the diameter of the residue and the diameter of the original particle.

Interferences

In Eagle River Flats sediments, an orange residue may be left by iron fragments and by some

invertebrates that live in the sediments. For example, the burned remains of the midge larvae

Chironomus sp., commonly called blood worms,

were mistaken for the orange residue left by WP

particles. For a test to be considered positive for

white phosphorus, the observations should require both a flame and the formation of orange

residue. Adherence to these criteria should eliminate most false positives.

Figure 5. Map showing that WP concentrations and

boundaries of six 7.5-m × 20-m areas where composite

samples were taken and analyzed by the field test.

Figure 4. Technician in field examining samples for

evidence of WP particles.

6,801,290

6,801,310

6,801,330

6,801,350

6,801,370

354,980 355,000 355,020 355,040 (m)

North

East

> 1 μg/g

0.1 to 0.99 μg/g

0.001 to 0.099 μg/g

< 0.001 μg/g

Not Detected

1

2

3

4

5

6

(m)

5
tained. Following analysis by headspace SPME, a

10-mL aliquot of isooctane was added to each

sample jar, and the samples shaken for 18 hours.

A 1-μL aliquot of the isooctane extract was injected into the gas chromatograph. The mass of white

phosphorus detected per injection by each method was calculated based on external calibration

standards. The mass found in the 1 μL of isooctane was also used to calculate the concentration

in μg/g (Table 3). For the three samples where

the white phosphorus concentration was greater

than 0.5 μg/g, two additional 40-g subsamples

were spread across the bottom of an aluminum

pie plate and heated.

The amount of WP detected in the headspace

of each sample by SPME correlated well with that

found by solvent extraction. Of the 19 samples

tested, 13 were negative by both methods. For the

six positive samples, the amount of WP detected

by SPME was proportional to that found by solvent extraction, i.e., the highest masses of WP

detected were for those samples with the highest

concentration. Both methods were comparable in

detection capability. The certified reporting limit

(CRL) of the solvent extraction procedure is

0.00088 μg/g. The lowest concentration detected

in the positive samples was slightly greater than

the CRL (0.00094 μg/g), and SPME also gave a

positive result for this sample. Future work on

the SPME procedure will be to attempt to calibrate for quantitative results.

For those samples that were subjected to the

2

4

6

8

0 0.5 1.0 1.5 2.0

y = –0.80875 + 3.9172x

Diameter of Orange Residue (mm)

WP, Particle Diameter (mm)

r2 = 0.90301

Figure 6. Diameters of orange residue left by WP

particles of known diameter after placement in a

smear of mud on an aluminum pie plate and heating

until water evaporates.

The orange residue produced from WP is acidic and rich in orthophosphate. However, the sediment at ERF is highly buffered and is also rich in

orthophosphate. Therefore efforts were unsuccessful to confirm a positive field test measuring

pH or orthophosphate.

SPME and future work

The field screening approach described in this

report is simple, quick and unsophisticated. Positive results were obtained for samples where the

laboratory method indicated WP concentrations

above 1 μg/g. We next tested a SPME procedure

(Fig. 7) to allow detection of lower concentrations

of WP without solvent extraction. This procedure

does require the use of a gas chromatograph; therefore, field personnel would need to be trained in

GC setup and maintenance. A series of discrete

sediment samples were collected from Eagle

River Flats. For each sample, a 40-g wet subsample and 10 mL of reagent grade water were placed

in a 120-mL jar equipped with a septum cap. The

jars were sealed and manually shaken 10 times so

that the sample was well mixed and coated the

sides of the jar. Samples stood at room temperature (20°C) for one hour, and then each sample

was analyzed as follows. The jar was shaken an

additional 10 times, and the SPME fiber was exposed to the headspace for 5 min. Immediately

following exposure to the headspace, the SPME

fiber was inserted into the injection port of the

gas chromatograph, and a chromatogram obFigure 7. Solid phase micro-extraction (SPME) of a sediment sample

to test for the presence of white phosphorus. Following exposure to the headspace above the sample, the

SPME phase is transferred directly to the injection

port of the gas chromatograph.

SPME Holder

40 g Sediment 

Plus Water

Headspace

SPME Phase

6
and the assumption that each particle was spherical. WP concentrations for the samples where comparison was possible were estimated and found

to be of the same order of magnitude as that

obtained by the laboratory method. Since the presence or absence of one millimeter-size particle in

a subsample would completely change the conhot plate field test, WP particles were detected in

two out of the three samples (Tables 3 and 4). The

diameter of the residue left by each particle was

measured, and the equation presented in Figure 6

used to estimate the diameter of each WP particle

prior to burning. The total mass of the WP was

estimated based on the density of WP (1.82 g/mL)

Table 3. WP detected by solvent extraction, SPME and field test.

Hot plate field test

Number of Diameter of

WP conc. WP mass (pg) detected particles residue

Sample* ID (μg/g)† Isooctane** SPME detected (mm)

BT-CC-1a 0.00094 3.8 6.0

old 248 0.0015 6.0 3.6

old 250 0.031 120 140

CP-CC-02†† 0.55 2,200 >5,400 0

MHB site†† 9.52 38,000 >11,000 7 0.4–3.7

CP-CC-01†† 70.1 280,000 >11,000 1 3.5

CP-CC-03 <0.00088 ND ND

CP-CC-04 <0.00088 ND ND

CP-CC-05 <0.00088 ND ND

CP-CC-06 <0.00088 ND ND

CP-CC-07 <0.00088 ND ND

CP-CC-08 <0.00088 ND ND

CP-CC-09 <0.00088 ND ND

MHR site <0.00088 ND ND

MW site 1 <0.00088 ND ND

MW site 2 <0.00088 ND ND

MW site 3 <0.00088 ND ND

MW site 4 <0.00088 ND ND

MW site 5 <0.00088 ND ND

* Same sample used for isooctane extraction and SPME.

† WP concentration determined by isooctane (10 mL) extraction of 40-g sediment sample.

** WP mass detected in 1-μL aliquot of 10-mL extract. †† Samples were overrange. Isooctane extracts diluted to within linear range.

ND = Not detected

Table 4. Estimation of WP concentration based on the number and

diameter of WP particles detected by field method.

Diameter Estimated* WP Estimated† Estimated**

of residue particle diameter mass of WP WP conc.

Sample (mm) (mm) particle (mg) (μg/g)

CP-CC-01 3.5 1.1 1.3 16.0

MHB site 3.7 1.2 1.5

1.6 0.6 0.2

1.5 0.6 0.2

1 0.5 0.09

0.6 0.4 0.04

0.6 0.4 0.04

0.4 0.3 0.03

26.1

Sum for MHB site = 2.1

* Asuming each particle is a sphere.

† Density of WP is 1.82 g/mL

** Based on 80 g of sediment (two 40-g subsamples).

7
centration estimate, we can never expect excellent quantitative agreement.

Each screening method has certain advantages.

The hot plate field test requires minimal training

and equipment, but detection capability is limited to samples containing millimeter-size particles of white phosphorus. Also, for some sites

where the identity of contaminants is unknown,

heating a sample might not be prudent in terms

of safety. The SPME approach provides much

greater sensitivity than the hotplate method, but

requires a gas chromatograph and an analyst

trained in GC operation and maintenance.

CONCLUSIONS

A simple field-screening method to detect white

phosphorus particles is described. The method is

based on the visual detection of the inflammation

of white phosphorus particles at relatively low

temperatures (less than 40°C) once a protective

layer of water is removed. The field screening

method consistently gave positive results for samples where the laboratory method indicated WP

concentrations above 1 μg/g. It also gives some

idea of the size and number of particles. The number of false positives were few if the criteria for a

test to be considered positive are the observations

of 1) a localized area of intense smoke and/or

flame and 2) the formation of orange residue.

A more sophisticated technique, based on solidphase microextraction and GC determination,

was tested and found to be comparable in detection capability to the laboratory method.

LITERATURE CITED

Daasch, L.W., J.N. Weber, M.A. Ebner and G.

Sparrow (1969) Mass spectra of phosphorus and

phosphorus oxides. Journal of Mass Spectrometry

and Ion Physics, 2: 503–505.

Gilbert, R.O. (1987) Statistical Methods for Environmental Pollution Monitoring. New York: Van

Nostrand Reinhold.

Racine, C.H., M.E. Walsh, C.M. Collins, D.J.

Calkins, B.D. Roebuck and L. Reitsma (1992)

Waterfowl mortality in Eagle River Flats, Alaska:

The role of munitions residues. USA Cold Regions Research and Engineering Laboratory,

CRREL Report 92-5.

Racine, C.H., M.E. Walsh, C.M. Collins, L. Reitsma and B. Steele (1993a) Sampling and site assessment of white phosphorus sediment contamination in ponds of an Alaskan salt marsh. Society

of Environmental Toxicology and Chemistry, 14th

Annual Meeting, 14–18 November, Houston, Texas.

Racine, C.H., M.E. Walsh, C.M. Collins, S.T.

Taylor, B.D. Roebuck, L. Reitsma and B. Steele

(1993b) Remedial investigation report for white

phosphorus contamination in an Alaskan salt

marsh. USA Cold Regions Research and Engineering Laboratory, CRREL Report 93-17.

Simmers, J.W., R.A. Price and S. Stokke (1994)

Assessment of white phosphorus storage in wetlands within the artillery impact area of Ft. McCoy. In Proceedings of the 18th Annual Army Environmental Technology Symposium, 28–30 June 1994,

Williamsburg, Virginia. Sponsored by the U.S. Army

Environmental Center.

Walsh, M.E. (1995) Analytical method for white

phosphorus in water. Bulletin of Environmental Contamination and Toxicology, 54: 432–439.

Walsh, M.E. and C.M. Collins (1993) Distribution of white phosphorus residues from the detonation of 81-mm mortar WP smoke rounds at an

upland site. USA Cold Regions Research and Engineering Laboratory, Special Report 93-18.

Walsh, M.E. and S.T. Taylor (1993) Analytical

method for white phosphorus in munitions-contaminated sediments. Analytica Chimica Acta, 282:

55–61.

Zhang, Z. and J. Pawliszyn (1993) Headspace

solid-phase microextraction. Analytical Chemistry,

65: 1843–1852.

8
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October 1995

Simple Field Screening Method for White Phosphorus (P4) in Sediment

Marianne E. Walsh, Charles H. Racine, Charles M. Collins,

Carl Bouwkamp and Philip G. Thorne

U.S. Army Cold Regions Research and Engineering Laboratory

72 Lyme Road Special Report 95-25

Hanover, New Hampshire 03755-1290

U.S. Army Environmental Center

Aberdeen Proving Ground, Maryland 21010-5401 SFIM-AEC-ETD-CR-95040

Approved for public release; distribution is unlimited.

Available from NTIS, Springfield, Virginia 22161

14

Field screening Waterfowl

Sediment sampling White phosphorus

UNCLASSIFIED UNCLASSIFIED UNCLASSIFIED UL

A simple field screening method to detect white phosphorus particles in sediment is described. A thin layer of wet

sediment is heated until all water evaporates. The presence of white phosphorus is indicated by visual detection

of the inflammation of white phosphorus particles that occurs at relatively low temperatures (less than 40°C) once

a protective layer of water is removed. The field screening method consistently gave positive results for samples

where solvent extraction followed by gas chromatography indicated white phosphorus concentrations above 1

μg/g. A more sophisticated method, based on solid-phase microextraction and gas chromotography determination, was also tested. Concentrations less than 1 μg/kg were detectable.