marianne e. walsh and michael r. walsh charles a. ramsey
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Marianne E. Walsh and Michael R. Walsh
Charles A. Ramsey
• Live-fire of high explosive ordnance onto repeatedly-used training ranges
• Potential accumulation of energetic residues
• Source for groundwater contamination and off-site migration
Nitramines: RDX, HMX
Nitroaromatics: TNT
Comp B (RDX/TNT)
Nuggets of C4 (RDX)
105-mm Howitzer
Fibers 0.4 to 7.5 mm long containing 2,4-DNT
Anti-tank Rocket (AT-4)
38% of propellant residue mass is NG
NO 2
CH 3
NO 2
HC-O-NO2
H2C-O-NO2
H2C-O-NO2
2,4-Dinitrotoluene (2,4-DNT)
Nitroglycerin (NG)
• The sampling procedure must minimize the error due to the heterogeneous sizes, compositional variability, and spatial distribution of the energetic particles.
• Samples must have sufficient mass to include all constituents in the same proportions as the soil surface
• Multi-increment samples composed of a minimum of 50 soil aliquots.
How Much Mass is Enough?
http://www.epa.gov/osw/hazard/testmethods/sw846/new_meth.htm#8330B
At the analytical lab, a small mass of soil is used to estimate the mean concentration in the field sample that is likely to be a kilogram or more, which in turn ideally represents the mean concentration at the field site.
Decisions are made about tons of soil based on a concentration estimate from a few grams of soil.
Air-dry Sieve using 2-mm mesh Particle size reduction
Grind for the appropriate amount of time without heating the sample
Subsample Many increments (>30) through the thickness of the
sample
Solvent extraction with acetonitrile Analysis using HPLC-UV
• Drying arrests microbial activity and enhances further processing prior to subsampling
• Oven drying not acceptable due to thermal degradation and/or sublimation of semi-volatile analytes
• Analyte concentrations in field-contaminated air-dried soils are stable at room-temperature.
Soil Initial
Processing
Date 1st
Analyzed
1st Conc.
Estimates*
(mg/kg)
2005 Results*†
mg/kg
Milan AAP 10 Mesh sieve
1999 RDX 23 ± 10
HMX 4 ± 1
RDX 29 ± 0.3
HMX 6.6 ± 0.1
Volunteer
AAP
Manual grind,
30 mesh sieve 1995
TNT 10.5 ± 0.3
DNT 1.4 ± 0.04
TNT 10.2 ± 0.3
DNT 2.7 ± 0.08
Fort Lewis
Hand
Grenade
Range
None 2001
Co-located sample
RDX 3.8 ± 1.8
HMX 1.0 ± 0.24
TNT 1.4 ± 0.88
Co-located sample
RDX 3.8 ± 0.08
HMX 0.95 ± 0.01
TNT 0.96 ± 0.05
* n ≥ 3 † Samples mechanically ground
• EPA SW-846 Method 8330 specified a 2-g subsample of a soil sample that has been manually ground with a mortar and pestle to pass through a #30-mesh (0.595 mm) sieve.
• Is this sieve size appropriate for training range soils?
Size Fraction Soil RDX TNT
>2 mm (#10-mesh) 257 g (21%) 6.2 µg (0.3%) 58 µg (0.8%)
>0.595 mm and < 2 mm 243 g (20%) 1,540 µg (66%) 5130 µg (74%)
<0.595 mm (#30-mesh) 713 g (59%) 786 µg (34%) 1,780 (26%)
>2 mm 188 g (17%) 4.3 µg (1.1%) 67 µg (5.6%)
>0.595 mm and < 2 mm 212 g (19%) 151 µg (40%) 708 µg (59%)
<0.595 mm 711 g (64%) 224 µg (59%) 420 µg (35%)
>2 mm 239 (14%) 7.2 µg (0.2%) 23 µg (1.8%)
>0.595 mm and < 2 mm 302 (18%) 2,050 µg (49%) 1,024 µg (77%)
<0.595 mm 1,183 (69%) 2,110 µg (51%) 275 µg (21%)
Size Fractionation of Three Soils from a Hand Grenade Range
Mass in Fraction (% of Total Mass)
Size Fraction Soil 2,4-DNT
>2 mm 1,870 g (44%) <d (0%)
>0.595 mm and < 2 mm 800 g (19%) 1,510 µg (69%)
<0.595 mm 1,610 g (38%) 680 µg (31%)
>2 mm 1,260 g (43%) <d (0%)
>0.595 mm and < 2 mm 500 g (17%) 1,650 µg (73%)
<0.595 mm 1,160 g (40%) 600 µg (27%)
>2 mm 1,600 g (43%) <d (0%)
>0.595 mm and < 2 mm 610 g (17%) 780 µg (61%)
<0.595 mm 1,470 g (40%) 500 µg (39%)
Size Fractionation of Three Soils from a 105-mm Firing Point
Mass in Fraction (% of Total Mass)
RDX Conc. (mg/kg) TNT Conc. (mg/kg)
Subsample 2-g 50-g 2-g 50-g
1 2.36 1.68 0.39 0.25
2 0.98 1.77 0.48 1.81
3 4.26 1.46 0.37 0.37
4 2.08 3.80 0.41 1.48
5 2.85 7.83 28.6 7.93
6 1.65 1.81 0.48 0.56
7 1.24 2.35 0.45 0.35
8 2.30 2.51 0.68 0.75
9 1.23 2.08 0.77 0.56
10 8.49 1.98 1.08 0.35
11 2.28 1.68 0.77 0.62
12 2.62 13.0 0.47 5.62
Particle Size Reduction by Machine Grinding on a Puck Mill
• The multi-increment sample will contain very few energetic particles or propellant fibers compared to the total soil matrix.
• Grinding reduces the particle size of the course soil to the texture of flour (<75 μm) and vastly increases the number of particles.
RDX Conc. (mg/kg) TNT Conc. (mg/kg)
Subsample Not Ground Ground Not Ground Ground
1 1.68 4.75 0.25 2.03
2 1.77 4.71 1.81 2.04
3 1.46 4.80 0.37 2.00
4 3.80 4.73 1.48 2.03
5 7.83 4.67 7.93 1.97
6 1.81 4.66 0.56 2.00
7 2.35 4.62 0.35 1.90
8 2.51 4.62 0.75 2.02
9 2.08 4.64 0.56 1.97
10 1.98 4.69 0.35 1.98
11 1.68 4.66 0.62 1.90
12 13.0 4.60 5.62 1.91
*50-g subsamples.
Subsampling Variance following Grinding for 60 s of Training Range Soils
Concentration (mg/kg)
Training Range Analyte Lab Rep 1 Lab Rep 2 Lap Rep 3 RSD
Hand Grenade
(10-g subsamples)
HMX 1.68 1.66 1.61 2.1%
RDX 10.9 10.6 10.4 2.4%
TNT 1.32 1.28 1.18 5.6%
Anti-Tank
(10-g subsamples)
HMX 410 382 404 3.7%
TNT 5.02 4.68 4.98 3.8%
NG 0.57 0.45 0.83 32%
Artillery/Mortar Impact
Area
(10-g subsamples)
HMX 1.49 1.44 1.48 1.8%
RDX 12.8 12.5 13.0 2.0%
TNT 4.78 4.86 4.80 0.86%
105-mm Firing Point
(60-g subsamples)
2,4-DNT 0.35 0.41 0.66 35%
2,4-DNT 1.1 0.61 2.34 66%
Fibers 9% DNT
1 m
m
120-mm Mortar
Flakes 36% NG
Rings or fragments 10% NG
Nitrocellulose propellant is fibrous and does not disaggregate like crystalline explosives. Soils must be ground for five 60-s cycles
Slide courtesy of Larry Penfold, TestAmerica
Subsampling and Solvent Extraction of Machine-Ground Soils Containing Energetics
Sonic Bath
Shaker Table
Yes, if the sample is processed correctly!
Concentration (mg/kg) Soil from a Demolition Training Range Mass (g) Extracted HMX RDX 2,4-DNT 10 g (Rep 1) 1.98 11.7 4.6 10 g (Rep 2) 2.00 11.6 4.9 10 g (Rep 3) 1.98 11.8 5.2 1770 g (Rest of sample) 2.02 11.9 4.8 Soil from an Artillery Impact Area Mass (g) Extracted HMX RDX TNT 10 g (Rep 1) 2.72 14.1 1.60 10 g (Rep 2) 2.72 14.1 1.60 10 g (Rep 3) 2.60 13.9 1.63 1300 g (Rest of sample) 2.76 14.3 1.56
Air-drying Isolate high concentration samples to prevent cross contamination
Sieving Use appropriate mesh size
No Splitting Process entire sample
Particle size reduction Grind for the appropriate amount of time without heating the sample
Subsampling Take many increments (>30) through the thickness of the sample
Solvent extraction Shaker table extraction is an acceptable alternative to the sonic bath extraction Some soils (clays) may require extended (>18 hrs) extraction time
Lab Analytical Methods
•Method 8330 (Nitroaromatics and Nitramines by High Performance Liquid Chromatography (HPLC))
- UV Detector (update of method will incorporate MS) - Detection limits around 0.05 mg/kg •Method 8095 (Nitroaromatics and Nitramines by Gas
Chromatograph(GC)) - Electron Capture Detector - Detection limits less than 0.010 mg/kg for TNT and RDX
Sample processing is the same for both methods.
HPLC-UV Instrumentation
Column: Waters Nova-Pak C8
60Å 4µm
3.9 X 150mm
Eluent: 1.4 mL/min
15:85 2-Propanol:Water
28°C
Detector:
ThermoSeparations Products
Spectra System UV2000
Dual Wavelength
254 nm and 210 nm
Chromatogram (HPLC-UV) Calibration Standard
HPLC-UV Chromatograms from a Multi-increment Sample†: Duplicate 10-g Subsamples
†Sample Mass: 1860 g
HMX 2.1 mg/kg
RDX 10 mg/kg
TNT 2.7 mg/kg
HMX 2.0 mg/kg
RDX 10 mg/kg
TNT 2.6 mg/kg
HMX
RDX
TNT HMX
RDX
TNT
Peak heights for HMX, RDX, and TNT are almost identical in the two chromatograms
Chromatogram (GC-µECD) Calibration Standard
0
1000
2000
3000
4000
5000
6000
0 2 4 6 8 10 12 14
Sig
nal
(Hz)
Time (min)
NB
NG
1,3
-DN
B2
,6-D
NT
2,4
-DN
T
TN
BT
NT
PE
TN
RD
X
4-A
m-D
NT 2
-Am
-DN
T
Tetr
yl
HM
X
NT
s
100 µg/L Standard
3,5
-DN
A
Chromatogram (GC-µECD) 81-mm Mortar Impact Area
500
1,000
1,500
2,000
2,500
5 10 15
Time (min)
Sig
nal (H
z)
RD
X (
95 µ
g/k
g)
HM
X (
620 µ
g/k
g)
HPLC-UV More rugged
Better reproducibility (smaller analytical error)
GC-ECD Lower detection limits for most analytes
Determination of nitramines and nitrate esters requires
constant injector maintenance
Appropriate for soils with explosives concentrations
ranging from 1 to 100 µg/kg
Good method for confirmation, but not rugged
•The entire sample received by an analytical lab must be processed (not just a small portion off the top).
•Field sampling and laboratory subsampling error cannot be ignored.
•Appropriate analytical method must be used. Standard methods for semi-volatiles ARE NOT appropriate for explosives and propellants.
•New methods and procedures need to be verified using field soils.
Tons of Soil 3 mg/kg RDX
Kilograms of Soil 3 mg/kg RDX
10 g of soil 3 mg/kg RDX
100 µL of solvent analyzed
Solvent Extraction 0.03 mg RDX
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