Update on ESTCP Project ER-0918: Field Sampling and Sample Processing for Metals on DoD Ranges Jay L. Clausen US Army Corps of Engineers, ERDC CRREL
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Project Team Jay L. Clausen, PI: ERDC-CRREL Anthony Bednar: ERDC-EL Thomas Georgian: HNC@EMCX Larry Penfold: Test America Diane Anderson: APPL Laboratories 2
Technical Objectives Demonstrate improved data quality for metal constituents in surface soils on military training ranges by coupling multi-increment sampling with modifications to sample preparation and analysis methods such as: Sample processing involving grinding Sub-sampling to build the digestate aliquot Digestion Issues (mass, acid ratio, time) Laboratory processing protocol applicable to both metals and energetics 3
Experimental Design Task 1 Multi-increment versus grab samples Number of increments per decision unit Grinding necessity Digestion mass evaluation Digestion time Blank material identification and assessment Puck Mill metal carry over assessment (cross contamination) Grinder comparisons Puck Mill and Roller Mill optimum grinding interval Appropriateness of field splitting Subsampling for digestate preparation 4
Experimental Design Task 1 Task 1 Activities Task 4 Activities Single DU FP Berm MI Sample Pb ~ 400 Note: Each level consists of 15 replicates Sample Type Grab Sample MI Sample Sample Type Soil Grab Concentration Sample (mg/kg) Pb < 400 50 50 Number of Increments 5 10 20 30 Pb > 400 50 100 200 Grinding Necessity Unground Ground Field Splitting Appropriateness Grinding Necessity Unground Grinder Type MP Puck Mill Roller Mill Pulvisette Puck and Ring Mill Grinder Type MP Puck Mill Ground Puck and Ring Mill Pulvisette Roller Mill Grinding Variability Between Field Reps. Within Sample Reps. Grinding Interval (min) 0.5 1 1.5 2 5 480 720 960 1200 Number Subsampling Increments 10 20 30 50 100 Digestion Time (hrs) 24 48 Digestion Mass (g) 0.5 1 2 5 10 5
Soil Test Material Site: Camp Ethan Allen, VT Range Type: Small Arms (Pistol, Rifle) Decision Unit: Berm Face 3 by 30 m Soil Type: Silty sand, low CEC, low OM, ph~ 5 Metal Content: 100 s to low 1,000 s ppm Samples Collected Grab/discrete using grid-node approach 30 Multi-increment using systematic random, 7 replicates of 5, 10, 20, 30, 50, 100 increments One 200 increment sample ~ 25 kg 6
Soil Test Material 7
Multi-Increment vs Grab Samples Sb mg/kg Cu mg/kg Pb mg/kg Zn mg/kg Grab Mean 88 300 5060 66 (n=30) Std. Dev. 375 132 14,437 17.5 RSD (%) 426 44 285 27 MI-30 Mean 23 573 2664 67 (n=7) Std. Dev. 3.3 85 367 4.0 RSD (%) 14 15 14 6 MI-50 Mean 17.6 457 2156 67 (n=7) Std. Dev. 1.8 96 243 6.5 RSD (%) 10 21 11 10 8
mg/kg StDev 3500 3000 2500 2000 1500 1000 500 0 Number of Increments per Decision Unit Scatterplot of StDev vs Increments Variable Al Ba Cd Co Cr Cu Fe Mg Mn Ni P Pb Sb Sr V W Zn 0 20 40 60 Increments 80 100 9
Number of Increments per Decision Unit 4500 Boxplot of Pb (mg/kg) by Number of Field Increments Pb (mg/kg) 4000 3500 3000 2500 2000 Medians 95 th Percentile Range IQR 1500 1000 5 10 20 30 Number of Field Increments 50 100 10
Grinding Necessity Sb mg/kg Cu mg/kg Pb mg/kg Zn mg/kg Un- Ground Mean 14 360 1600 66 (n=15) Std. Dev. 10 90 630 11.3 RSD (%) 71 25 39 17 Ground Mean 23 550 2720 77 (n=15) Std. Dev. 1.6 100 120 8.7 RSD (%) 7.0 18 4.4 11 Performance criteria RSD < 15% for lab replicates (for concentrations > 100 11
Soil Post Grinding 12
Grinding Necessity mg/kg 3500 3000 2500 95 th Percentile Range Boxplot of Pb by Method Outlier Pb 2000 1500 Medians IQR 1000 G Method UG 13
Performance Assessment Sample Processing (Grinding) of Soil Puck Mill Roller Mill Pulvisette Fe, Mn, Cr, V Alumina cans polyethylene Liner, ceramic balls Mortar and Pestle Ceramic Agate balls 14
RSD (%) Grinder Comparisons 2200 15
Grinder Comparisons 25000 Boxplot of Pb (mg/kg) by Grinder Type 20000 Pb (mg/kg) 15000 10000 5000 0 Ball Mill-16 Ball Mill-20 Puck Puck Ring Grinder Type Pulvisette UG-EL UG-TA 16
RSD (%) Roller Mill Optimum Grinding Interval 17
mg/kg Roller Mill Optimum Grinding Interval 18
Roller Mill Optimum Grinding Interval 7500 Boxplot of Pb (mg/kg) by Grinder Type 7000 6500 Pb (mg/kg) 6000 5500 5000 4500 Increasing Grinding time (hrs) 4000 Ball Mill-08 Ball Mill-12 Ball Mill-16 Grinder Type Ball Mill-20 19
Digestion Mass Scatterplot of StDev vs Mass 0 5 10 0 5 10 StDev 500 250 0 500 250 0 0 Al Ba Cd Co Cr Cu Fe Mg Mn Ni P Pb Sb Sr V W Zn 0 5 10 0 5 10 5 10 Mass 500 250 0 500 250 0 Variable Al Ba Cd Co Cr Cu Fe Mg Mn Ni P Pb Sb Sr V W Zn Panel variable: Variable 20
Digestion Time Metal M 24 (mg/kg) M 48 (mg/kg) Metal M 24 (mg/kg) M 48 (mg/kg) Al 5678 6075 Mn 223.9 242.8 Ba 30.29 32.09 Ni 12.24 11.67 Cd 1.825 1.050 P 612.3 630.0 Co 8.60 8.935 Pb 2718 2893 Cr 221.2 242.1 Sb 22.61 20.59 Cu 542.5 498.2 Sr 21.51 23.80 Fe 16920 17293 V 15.14 16.32 Mg 2121 2259 Zn 75.80 79.88 M 24, M 48 = Median 24- and 48-hr digestions, respectively 21
Issues Analysis error is still greater than expected between laboratories, believed associated with volume of acid used during digestion Considerable mass of metal remains in over size fraction (typically discarded) Ongoing question of impact of sample preparation method changes to risk determination Poor recovery of antimony is evident with conventional analysis; new digestion process needed 22