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Ground Water Sampling at ISCO Sites Ground Water Sampling at ISCO Sites – Ground Water Sampling at ISCO Sites – Ground Water Sampling at ISCO Sites – Oxidant – Oxidant Oxidant Oxidant R R Residuals and Sample Preservation Guidelines Residuals and Sample Preservation Guidelines Residuals and Sample Preservation Guidelines Residuals and Sample Preservation Guidelines R R id id id id l l l l d S d S d S d S l l l l P P P P ti ti ti ti G id li G id li G id li G id li National Association of National Association of National Association of National Association of Remedial Project Managers Remedial Project Managers Remedial Project Managers Remedial Project Managers Kansas City, KS Kansas City, KS Kansas City, KS Kansas City, KS May 19, 2011 May 19, 2011 May 19, 2011 May 19, 2011 Scott G. Huling Scott G. Huling Scott G. Huling Scott G. Huling USEPA R S Kerr Environmental Research Center USEPA R S Kerr Environmental Research Center USEPA R.S. Kerr Environmental Research Center USEPA R.S. Kerr Environmental Research Center Ada, OK Ada, OK

Collaborators: Collaborators: Collaborators: Collaborators: Saebom Ko Saebom Ko Saebom Ko Saebom Ko National Research Council National Research Council National Research Council National Research Council Robert S. Kerr Environmental Research Center (Ada, OK) Robert S. Kerr Environmental Research Center (Ada, OK) Robert S. Kerr Environmental Research Center (Ada, OK) Robert S. Kerr Environmental Research Center (Ada, OK) Bruce Pivetz Bruce Pivetz Bruce Pivetz Bruce Pivetz Shaw Environmental & Infrastructure, Inc. Shaw Environmental & Infrastructure, Inc. Shaw Environmental & Infrastructure, Inc. Shaw Environmental & Infrastructure, Inc. Robert S. Kerr Environmental Research Center (Ada, OK) Robert S. Kerr Environmental Research Center (Ada, OK) Robert S. Kerr Environmental Research Center (Ada, OK) Robert S. Kerr Environmental Research Center (Ada, OK) Rob Weber, Karen T. Johnson, Margerie St. Germain, Rob Weber, Karen T. Johnson, Margerie St. Germain, Rob Weber, Karen T. Johnson, Margerie St. Germain, Rob Weber, Karen T. Johnson, Margerie St. Germain, Nancy Swyers, Brad Vann, DeAndre Singletary Nancy Swyers, Brad Vann, DeAndre Singletary Nancy Swyers, Brad Vann, DeAndre Singletary Nancy Swyers, Brad Vann, DeAndre Singletary y y y y y y y y , , , , , , , , g g g g y y y y EPA Region 7 EPA Region 7 (Kansas City, KS) EPA Region 7 EPA Region 7 (Kansas City, KS) (Kansas City, KS) (Kansas City, KS)

“Binary Mixtures” “Binary Mixtures” • Ground water samples collected specifically to be analyzed • Ground water samples collected specifically to be analyzed G G d d t t l l ll ll t d t d ifi ifi ll ll t t b b l l d d for organic contaminants; may contain a mixture of both for organic contaminants; may contain a mixture of both the contaminant and the oxidant. the contaminant and the oxidant. • Issue raised many times in the past, including • Issue raised many times in the past, including  Savage Well, Olympia (Wells G&H) (Region 1)  Savage Well, Olympia (Wells G&H) (Region 1)  Vieques PR (Region 2)  Vieques PR (Region 2)  Fike/Artel, Berks Sand Pit (Region 3)  Fike/Artel, Berks Sand Pit (Region 3)  Southern Solvents (Region 4)  Southern Solvents (Region 4) S S th th S l S l t t (R (R i i 4) 4)  Parkview (Region 7)  Parkview (Region 7) • Preliminary review • Preliminary review • Preliminary review • Preliminary review  Definitive published information - Limited  Definitive published information - Limited  ISCO Analytical  ISCO Analytical ISCO, Analytical ISCO, Analytical

Overview Overview  Why / why not should binary mixtures be  Why / why not should binary mixtures be analyzed analyzed  Binary mixtures  Binary mixtures • How does this condition occur • How does this condition occur • Potential impact on ground water quality • Potential impact on ground water quality P P i l i i l i d d li li • Potential impact on analytical instrument • Potential impact on analytical instrument  Preservation techniques  Preservation techniques  Preservation techniques  Preservation techniques • Potential impact on ground water quality • Potential impact on ground water quality • Potential impact on analytical instrument • Potential impact on analytical instrument  Field test kits and methods  Field test kits and methods  Preliminary guidelines for preservation  Preliminary guidelines for preservation

Why collect and analyze a ground water Why collect and analyze a ground water sample that contains oxidant? sample that contains oxidant? p • Preliminary assessment of ISCO performance • Preliminary assessment of ISCO performance • Assess whether re-distribution of the contaminant • Assess whether re-distribution of the contaminant Assess whether re-distribution of the contaminant Assess whether re-distribution of the contaminant plume may have resulted from ISCO activities plume may have resulted from ISCO activities • Interim ISCO pilot-studies are implemented to • Interim ISCO pilot-studies are implemented to establish design parameters for full-scale ISCO establish design parameters for full-scale ISCO t bli h d t bli h d i i t t f f f ll f ll l l ISCO ISCO deployment (accelerated schedules) deployment (accelerated schedules) • Regulatory-driven goals and specified timelines • Regulatory-driven goals and specified timelines g g y y g g p p • Long term permanganate persistence (closure- • Long term permanganate persistence (closure- driven) driven) • Some decisions can be made (subsequent • Some decisions can be made (subsequent S S d d i i i i b b d d ( ( b b t t mobilization) mobilization) • Other reasons • Other reasons • Other reasons, … • Other reasons, …

Why not collect and analyze binary mixture Why not collect and analyze binary mixture ground water samples? ground water samples? ground water samples? ground water samples? • Oxidation of contaminants in sample • Oxidation of contaminants in sample • Ground water sample not representative of • Ground water sample not representative of subsurface conditions (non-equilibrium) subsurface conditions (non-equilibrium) • Some preservatives used to neutralize oxidant • Some preservatives used to neutralize oxidant S S  May impact quality of ground water  May impact quality of ground water • Dilution requirements to lower oxidant • Dilution requirements to lower oxidant Dil ti Dil ti i i t t t t l l id id t t concentration reduces detection limit to concentration reduces detection limit to unacceptable range unacceptable range unacceptable range unacceptable range

Oxidant Injection Well, Monitoring Well Point, or Other Oxidant Well Injection Method j TO SAMPLE FROM HYDRAULIC WELL CONDUCTIVITY LOW SANDY CLAY VERY CLAY CLAY LOW HIGH HIGH SAND SAND CLAYEY SAND MEDIUM LOW SANDY CLAY VERY HIGH SAND/GRAVEL VERY CLAY LOW

Oxidant Injection Well, Monitoring Well Point, or Other Oxidant Well Injection Method j HYDRAULIC CONDUCTIVITY LOW SANDY CLAY VERY CLAY CLAY LOW HIGH HIGH SAND CLAYEY SAND MEDIUM LOW SANDY CLAY VERY SAND/GRAVEL HIGH VERY CLAY LOW

1000 mg/L 100 mg/L 10 mg/L 10 mg/L 5 mg/L 1 mg/L 0 mg/L

1 PCE Oxidation 0.9 KMnO 4 oxidation of PCE KMnO 4 oxidation of PCE under homogeneous 0.8 conditions (Yan and Schwartz, 0.7 1999) 1999) PCE (20 C) PCE (10 C) 0.6 / C(o) 50% removal in 4-9 hours 0.5 0 5 C(t) / involving approximately 100 mg/L KMnO 4 0.4 0.3 Explains both PCE oxidation and PCE persistence 0.2 0.1 sample is “transient” 0 0 0 0.0 10 0 10.0 20 0 20.0 30 0 30.0 40 0 40.0 50 0 50.0 60 0 60.0 Time (Hours)

Table 1. First order transformation of chlorinate volatile organic compounds. 1 reaction rate 2 reaction rate contaminants Time required for 50% loss in constant, k (s -1 ) constant, k (s -1 ) contaminant in binary sample (hours) (20 O C) (20 O C) (20 O C) (10 O C) (20 O C) (10 O C) (10 O C ) (10 O C ) 4.5×10 -5 2.25×10 -5 PCE 4.3 8.6 6.5×10 -4 3.25×10 -4 TCE 0.3 0.6 9 2×10 -4 4 6×10 -4 c-DCE c DCE 9.2×10 4.6×10 0 2 0.2 0 4 0.4 3.0×10 -2 1.5×10 -2 t-DCE < 0.1 < 0.1 2.38×10 -3 1.19×10 -3 1,1-DCE 4.9 9.7 1 The first order reaction rate constant involved MnO 4 - at 1 mM (Yan and Schwartz The first-order reaction rate constant involved MnO 4 at 1 mM (Yan and Schwartz, 1999); rate constant adjusted for temperature (k 10 = k 20 / 2). Observations: 1. t-DCE detection doubtful in samples that contain MnO 4 - 2. 1,1-DCE is most resistant (5-10 hours) 3. Important to preserve sample with neutralizer if it is to be analyzed 4 Important not to analyze if it is not preserved 4. Important not to analyze if it is not preserved

Oxidant Injection Well, Monitoring Well Point, or Other Oxidant Well Injection Method j TO SAMPLE FROM HYDRAULIC WELL CONDUCTIVITY LOW SANDY CLAY VERY CLAY CLAY LOW HIGH HIGH SAND SAND CLAYEY SAND MEDIUM LOW SANDY CLAY VERY HIGH SAND/GRAVEL VERY CLAY LOW