EPA Method 8330B: Characterization of Energetic Residues EPA Method 8330B: Characterization of Energetic Residues on Military Training Rangeson Military Training Rangesy g gy g g

LiveLive--fire Test of 155fire Test of 155--mm Howitzermm Howitzer

Titan Booster Segment Disposal

ASTWMO Federal Facilities Managers Munitions Response Symposium

Alan D. HewittUSA Engineer Research and Development CenterCold Region Research and Engineering Laboratory

Hanover NH 03755 : 603-646-4385Alan.D.Hewitt@erdc.usace.army.mil

Major ParticipantsMajor ParticipantsSERDP ERSERDP ER--1155 and 1481, ESTCP ER1155 and 1481, ESTCP ER--06280628

• ERDC-CRRELERDC CRRELMarianne Walsh, Susan Taylor, Michael Walsh, Jay Clausen, Susan Bigl

• ERDC-ELERDC ELMark Chappell

• Defence R&D Canada - ValcartierSonia Thiboutot Guy Ampleman Sylvie Brochu Emmanuella DiazSonia Thiboutot, Guy Ampleman, Sylvie Brochu, Emmanuella Diaz, Richard Martel, Isabelle Poulin

• EnviroStatCh l RCharles Ramsey

Presentation OutlinePresentation OutlinePresentation OutlinePresentation Outline

• Data QualityData Quality

Sample handling & processingSample handling & processing

• Data Quality Q y

Discrete vs. MI samples – Upper p ppconfidence limit

http://www.epa.gov/epaoswer/hazwaste/test/pdfs/8330b.pdf

Method 8330B addresses: Method 8330B addresses: Residues at Firing PointsResidues at Firing PointsResidues at Firing PointsResidues at Firing Points

Howitzers

Mortars

Burning of40-mm Grenades

Burning of Excess

Propellant

Light Anti-Tank Weapons

Method 8330B addresses: Method 8330B addresses: Residues on Impact and Demolition Ranges: Residues on Impact and Demolition Ranges:

Example of a HighExample of a High--Order DetonationOrder Detonation

p gp gHigh Order & Low Order DetonationsHigh Order & Low Order Detonations

High Order Detonationp gp g High Order Detonation– Round detonates as designed– Metal fragments very small

R id d it d i– Residues deposited insub millimeter particles

Example of a Low-Order Detonation

Low Order DetonationLow Order Detonation– Round only partially detonates– Large metal pieces remain– Residues deposited in millimeter

to centimeter particles and chunks

Propellant and High Explosive residues are Propellant and High Explosive residues are deposited as particlesdeposited as particlesdeposited as particlesdeposited as particles

Fiber from105Fiber from105--mm Howitzermm Howitzer 8181--mm Low Order Detonationmm Low Order Detonation

1 mm

Comp BComp B(60% RDX / 39% TNT)(60% RDX / 39% TNT)

Fiber contained24 µg 2,42,4--DNTDNT 1 mm

MM--16 Small Arms16 Small Arms

µg ,,

TNTTNT

NGNG

100µm155155--mm Howitzer Roundmm Howitzer Round

Method 8330B: Method 8330B: Sampling and sample processingSampling and sample processingp g p p gp g p p g

Stratification oftraining rangeg g

Sampling strategyand design

Whole sample airdrying

Whole samplesieving

Whole samplepulverization p

Subsampling

Major Laboratory Changes: Major Laboratory Changes: Method 8330 >>> 8330BMethod 8330 >>> 8330BMethod 8330 >>> 8330BMethod 8330 >>> 8330B

• Determine analyte concentrations in the less than 2-mm ysize fraction in entire sample by using a #10 sieve to remove the oversize material.

• Machine grind (puck mill) soils from training ranges with high explosives for 60 s

M hi i d ( k ill) il f fi i i t d• Machine grind (puck mill) soils from firing points and demolition areas for five 60-s cycles

• Build 10 g analytical subsamples by combining at least 30• Build 10-g analytical subsamples by combining at least 30 increments of the ground field sample.

• Extract samples with 20 mL of acetonitrile on a platform• Extract samples with 20 mL of acetonitrile on a platform shaker or cooled sonic bath.

Solution for Energetic Residues: Particle Solution for Energetic Residues: Particle Size Reduction by Machine GrindingSize Reduction by Machine GrindingSize Reduction by Machine GrindingSize Reduction by Machine Grinding

Minimize fundamental error due to compositional heterogeneity

Does the Subsample Represent the Bulk Does the Subsample Represent the Bulk Sample ?Sample ?Sample ? Sample ?

* Primary Laboratory DQO* Primary Laboratory DQO

Comparison between Bulk and Comparison between Bulk and Average Subsample ConcentrationAverage Subsample Concentrationg pg p

Location Sample Soil wt (g) Acetone (mL) Concentration (mg/kg)

(After 8330B Processing)(After 8330B Processing)

HMXHMX RDXRDX TNTTNT 2,42,4--DNTDNTBulk 1766 3540 2.02 11.9 4.81

FRA Demo MI-9 R1 10.0 20.0 1.98 11.7 4.58R2 10 0 20 0 2 00 11 6 4 92R2 10.0 20.0 2.00 11.6 4.92R3 10.0 20.0 1.98 11.8 5.22

(Demolition Range) Ave 1.99 11.7 4.91Std Dev 0.009 0.090 0.320%RSD 0.48% 0.77% 6.53%

RPD (Bulk vs. Rep Ave) 1.5% 1.7% 2.1%

Bulk 1278 2560 2.76 14.3 1.56FRA LO# 3 MI-5 R1 10.0 20.0 2.72 14.1 1.60

R2 10.0 20.0 2.72 14.1 1.60(Impact Range) R3 10.0 20.0 2.60 13.9 1.63

Ave 2.68 14.0 1.61Std D 0 069 0 125 0 016Std Dev 0.069 0.125 0.016%RSD 2.59% 0.89% 1.00%

RPD (Bulk vs. Rep Ave) 3.1% 2.0% 3.2%

Comparison between Bulk and Comparison between Bulk and Average Subsample ConcentrationAverage Subsample ConcentrationAverage Subsample ConcentrationAverage Subsample Concentration

Location Sample Soil wt (g) Acetone (mL) Concentration (mg/kg)

(After 8330B Processing)(After 8330B Processing)

2,42,4--DNTDNT NGNGFt. Richardson Bulk 1196 2400 4.21

FP Fox R1 10.0 20.0 4.00MI-10 R2 10 0 20 0 5 04MI-10 R2 10.0 20.0 5.04

R3 10.0 20.0 4.06(Firing Point) Ave 4.37

Std Dev 0.584%RSD 13.4%

RPD (Bulk vs. Rep Ave) 3.7%

CFB Petawawa Bulk 1935 3880 0.964 2.97FP Juliet Tower R1 10.0 20.0 0.88 2.38FP Juliet Tower R1 10.0 20.0 0.88 2.38

140 MI-5 R2 10.0 20.0 1.09 2.84R3 10.0 20.0 1.17 3.36

(Firing Point) Ave 1.05 2.86Std D 0 152 0 490Std Dev 0.152 0.490%RSD 14.5% 17.1%

RPD (Bulk vs. Rep Ave) 8.5% 3.8%

Method 8330BMethod 8330B -- Laboratory DataLaboratory DataMethod 8330B Method 8330B Laboratory Data Laboratory Data QualityQuality

• 10 g subsamples are representative

• 10 g subsamples are an accurate assessment of• 10 g subsamples are an accurate assessment of bulk sample

Lab data is SCIENTIFICALLY DEFENSIBLE• Lab data is SCIENTIFICALLY DEFENSIBLE

Consequence of splitting sample in the field and/or taking subsample from top of sample container results in data that is only representative of subsample analyzedrepresentative of subsample analyzed.

Can Sample Splitting Address Subsampling Precision and Bias?Can Sample Splitting Address Subsampling Precision and Bias?Example: 2,4Example: 2,4--DNT Concentrations after DNT Concentrations after Rotary DivisionRotary Division of 11of 11--kg Samplekg Sample

1 40

Nugget effect: Shape / Density ?

1.20

1.40

g)

Deposited Propellant Fibers from 105 mm Howitzer

0.80

1.00

T C

onc

(µg/

g

0.40

0.602,

4-D

NT

Splits ≈ 0.9 kg

0.20.01 .1 1 5 10 2030 50 7080 9095 99 99.999.99

PercentNOT GROUND Mean 0.76 µg/g

Standard Deviation 0.21 µg/gRange 0.51 to 1.28 µg/g

NOT GROUND

What about Metals on Small Arms RangesWhat about Metals on Small Arms Ranges ??Concentration of metals < 2 mm FractionConcentration of metals < 2 mm Fraction

Earthen Backstop Earthen Backstop Firing LineFiring Line

PbPb

Bullets and bullet fragmentsBullets and bullet fragments Pb Pb -- Pistol Bullets Pistol Bullets

Selected results from Fort ShafterSelected results from Fort ShafterAirAir--dried, non ground, < 2dried, non ground, < 2--mm fraction split with mm fraction split with rotary dividerrotary divider: Modified Method 3050B, : Modified Method 3050B,

i.e.,10 g subsamples i.e.,10 g subsamples -- Analysis Method 6010BAnalysis Method 6010B

Subsample Metal Conc. (µg/g) Metals Conc. (µg/g)(replicates) Cu Pb Sb Cu

1 2650 360 5 51 99 499 41 2650 360 5.51 99.499.42 114114 329 4.98 90.23 305 915915 7.577.57 86.74 113 297 4 26 99 1

23x45

113131

297280

4.264.27

99.1126

6 135 2820 16.4 89.87 855 1650 11 6 88 2Nugget Effect ?7 855 1650 11.6 88.28 539 330 4.58 98.59 1190 846 4.18 83.210 126 1540 4 47 98 3

9.7x 4.4x 1 6x

gg

10 126 1540 4.47 98.311 1870 381 4.89 99.012 117 334 4.32 11313 128 291 3 73 80 2

1.6x

131415

128121112

291296820

3.734.108.24

80.287.183.8

Blue background - same sample

Impact of metal particles on laboratory Impact of metal particles on laboratory subsamples with and without pulverizationsubsamples with and without pulverization

Sieve # Cut off(particle size)

10 g Subsample(mg/kg)

2.0 g Subsample (mg/kg)

Pb #10 2.0mm 4800 24000

11.4 g/cc #18 1.0mm 600 3000

#60 0.25mm 9.3 47

Gro nd* 0 15mm 2 0 10Ground* 0.15mm 2.0 10

Cu #10 2.0mm 3800 19000

8.96 g/cc #18 1.0mm 470 2300

#60 0.25mm 7.3 37

Ground* 0.15mm 1.6 7.9

Sb #10 2 0 2800 14000Sb #10 2.0mm 2800 14000

6.68 g/cc #18 1.0mm 350 1700

#60 0.25mm 5.5 27

Ground* 0.15mm 1.2 5.9

* Entire sample, metal particles and matrix

Solution for Metals (?) : Grinding ESTCP ERSolution for Metals (?) : Grinding ESTCP ER--0918 0918

Whole samplepulverization Step #1(ceramic or agate)

Cleaning - Horizontal BICO pulverizer

Vertical BICO pulverizer

Malleable Metals (e.g. Pd, Cu, etc.) lost to surfaces ?

Ground sand <150 µm : 1 kg / min.

Sampling Data Quality: CFB PetawawaSampling Data Quality: CFB PetawawaJuliet TowerJuliet Tower –– a mounted vehicle firing pointa mounted vehicle firing pointJuliet Tower Juliet Tower –– a mounted vehicle firing pointa mounted vehicle firing point

D i i U it 30 30Ordnance found in sampling area Ordnance found in sampling area

at FP Juliet Towerat FP Juliet Tower

Decision Unit: 30-m x 30-m

What Do We Want to Know?What Do We Want to Know?

• Is mass of hazardous constituent in area of concern sufficient to present an unacceptable risk to ground water and surface water resources? (estimated from mean concentrationmean concentration in potential source zone)

• Is mean concentrationmean concentration present in the exposure unit above some risk criteria for target organisms on range?range?

Field Sampling Experiment: Estimating Field Sampling Experiment: Estimating mean concentrationsmean concentrationsmean concentrationsmean concentrations

MultiMulti--increment Samplingincrement SamplingDiscrete SamplingDiscrete Sampling

Path of travelCollection point for 100 discrete samples

Increment collection point for two separate MI samples

pTypically only a few discrete samples are collected

Distribution of NG Concentration Distribution of NG Concentration for individual samplesfor individual samplesfor individual samplesfor individual samples

Discrete Samples (n=100)100 Increment MI Samples (n=10)100-Increment MI Samples (n=10)

xDiscrete Sample StatisticsDiscrete Sample Statistics

x

Median

MI Sample StatisticsMI Sample StatisticsMI Sample StatisticsMedian

MI Sample StatisticsMI Sample StatisticsMI Sample Statistics

ESTCP ER-0628

NG Concentration (mg/kg) NG Concentration (mg/kg) -- Upper Confidence Upper Confidence LimitsLimits

U i t t l d t t d d l l t d b tU i t t l d t t d d l l t d b tUsing total data set and randomly selected subsetsUsing total data set and randomly selected subsets

10 M lti10 M lti i t S li t S l 100 Di S l100 Di S l10 Multi10 Multi--increment Samplesincrement Samples

Measured Concentration:Measured Concentration:95% UCL w/ ProUCL 3 0

100 Discrete Samples100 Discrete SamplesMeasured Concentration:Measured Concentration:– 95% UCL w/ ProUCL 4.9– 95% UCL w/ ProUCL 3.0

ProUCL Trials ProUCL Trials ––Number of 95% UCL w/

%ProUCL Trials ProUCL Trials ––Number of 95% UCL w/Samples ProUCL (5 trials )

Samples ProUCL (5 trials )

n = 4 3.2, 2.9, 2.8, 3.1, 3.2(100 incr.)

Samples ProUCL (5 trials )

n = 7 8.0, 22, 5.0, 7.3, 12n = 15 3.7, 4.6, 5.9, 2.5, 5.4n = 30 4 2 6 0 3 8 3 8 3 1

Range 2.3 to 3.2n = 30 4.2, 6.0, 3.8, 3.8, 3.1

G d t ti 2 79 /k2 79 /kGrand mean concentration: 2.79 mg/kg 2.79 mg/kg (25.8 kg of surface soil)

ESTCP ER-0628

Current Method 8330B and MIS GuidanceCurrent Method 8330B and MIS GuidancePublished

• Guidance for Obtaining Representative Laboratory Analytical Subsamples from Particulate Laboratory Samples (2003) - USEPA 600/R-03/027

• Method 8330B (2006) (http://www.epa.gov/epaoswer/hazwaste/test/pdfs/8330b.pdf)

• State of Hawaii (2008): Technical Guidance Manual: Chapters 3 & 4 (http://www.hawaiidoh.org/tgm.aspx?p=0402a.aspx)

• DoD EDQW (2008) “Guide for Implementing EPA SW 846 Method 8330”• DoD EDQW (2008) Guide for Implementing EPA SW-846 Method 8330 (http://www.navylabs.navy.mil/Archive/Final%208330B%20Implementation%20Guide%20070708.pdf)

Under development • United States Army, Military Munitions Response Program (Draft): Remedial

Investigation / Feasibility Study Guidance• US Army Corps of Engineers - Environmental and Munitions Center of

Expertise (Draft): Draft - Interim Guidance for Implementation of Multi-Expertise (Draft): Draft Interim Guidance for Implementation of Multiincrement Soil Sampling (MIS) for the Military Munitions Response Program

• AEC (In Prep): MMRP Guidance Document for Soil Sampling of Energetics• EPA FFF Issue paper (Under consideration) - Sampling Design and Analysis

f M iti R id R d O B /O D t ti (OB/OD)of Munitions Residues on Ranges and Open Burn/Open Detonation (OB/OD) Units

• ITRC (2009 Start) : Multi-increment Sampling (MIS) - 2009 Start