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Quantitative Metrics
to Gage the Effects
of an Enhanced
Biodegradation
Program
Iowa Army Ammunitions Plant,
Middletown, Iowa
Melisa Geraghty, Brian
Caldwell, PG; Dr. Tiffany
Downey, Dr. Ronnie Britto,
and Dr. Rick Arnseth
Site History
 Iowa Army Ammunition Plant (IAAAP) -
located in Des Moines County, Iowa
 Munitions production and testing beginning in
1941
 Resulted in contamination of the soil,
groundwater, and surface water with
explosives
– Extensive offsite Royal Demolition Explosive
(RDX) groundwater plume sourced by RDX in
surface water runoff.
 Off-Site Plume map here
Remediation Plan
 To enhance biodegradation and expedite the
natural attenuation of the RDX plume using an
enhanced degradation process (sodium acetate
injection)
– 11 designed-injection wells upgradient of the
highest concentration plume core.
– Analytically modeled injection rates and locations
– Five injection events between October 2007
and April 2009
• initial event employed all 11 injection wells.
• Subsequent events customized injected mass
and number of injection points based on
analytical data
Development of Evaluation Metrics
 Remedial progress metrics developed to
account for temporal and spatial comparisons
in order to maintain optimal reducing
conditions
– Quantitative analysis of plume configuration
– Statistical analysis of the RDX concentrations
from individual sampling events
Evaluation Metrics Include
 Point by point comparisons
– Statistical trend analysis
– First-order kinetics concentration change
analysis
• degradation rates and times to achieve
remediation goals.
 Plume wide analysis
– Representative population using differential
analysis
– Central Tendency Analysis
– Change in overall plume core mass.
Mann-Kendall Trend Analysis
 Non-parametric statistical test (the data are not
required to be normally distributed)
 Assesses point changes in a data set over time for an
increasing or decreasing trend at a given statistical
confidence level.
– Designed to assess four to eighteen rounds of data at
an 80% confidence level
– Determines if the data can be used to estimate a first
order degradation or augmentation rate
– To avoid biasing the MK test, the same value for all ND
results was used (one half of the detection limit from the
round with the lowest detection limit for that well).
– For wells that did not exhibit a increasing or decreasing
trend at an 80% confidence level the coefficient of
variation was used to determine if the well was stable or
unstable
Mann-Kendall Trend Analysis Con’t
 For wells that did not have a minimum of four
sampling events or did not exhibit an overall trend
at 80% confidence, the last three measurements
were used to approximate the direction of the
concentration change.
 The point-by-point analysis results indicate an
overall decreasing trend in a majority of the wells.
– 18 wells trended
• 8 = decreasing
• 1 = increasing
• 9 = stable
Quantifying a Decreasing Trend
 Plotting of the log-transformed concentrations versus a linear
unit of time (days were used). Finite source degradation is
described by an exponential degradation curve when plotted
on a linear scale. In order to use linear regression to calculate
the slope (the degradation rate), the data were log-
transformed and plotted on a linear scale.
 Performing linear regression calculations on Step 1 by plotting
a trend line (least-squares fit trend line) that minimizes the
variance (squared deviations) of all of the data points from the
line.
 Using the slope of the equation represented by the least-
squares trend line as the fractional change per day. This was
then used to calculate a half-life expressed in days, and to
develop a degradation curve that predicts the time at which
the concentrations at that sampling point will reach 2 ppb.
Example Output
DATE RDX (ug/L) Ln Conc. (ug/L)
Degradation Rate
(% per day)
09/28/2007 104 4.644390899 1.021765998
12/19/2007 95.8 4.562262685 1.003697791
02/13/2008 76.9 4.342505877 0.955351293
12/09/2008 41.3 3.7208625 0.81858975
First-order Degradation Rate (day-1) = 0.0022
Half Life (days) = 315.05
Mann Kendall Statistic (S) = -6.0
Number of Rounds (n) = 4
Average = 79.50
Standard Deviation = 27.880
Coefficient of Variation(CV)= 0.351
Trend ≥ 80% Confidence Level DECREASING
Trend ≥ 90% Confidence Level DECREASING
Example Output Graphs - Decreasing
y = -0.1440x + 5,771.5677
R² = 0.9731
0
20
40
60
80
100
120
RDXug/L
Date
EMW-06
y = -0.0022x + 90.2403
R² = 0.9880
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
LnRDXug/L
Date
EMW-06
0
5
10
15
20
25
30
35
40
45
0 200 400 600 800 1000 1200 1400 1600
Concentration(ug/L)
Time (days)
Degradation Curve
Example Output Graphs – Stable or
Non-Stable
y = 0.0144x - 506.6684
R² = 0.0769
0
10
20
30
40
50
60
70
RDXug/L
Date
IW-05
y = 0.0523x - 1,978.1657
R² = 0.9245
0
10
20
30
40
50
60
RDXug/L
Date
IW-05
Example Output Graphs - Increasing
y = 0.0035x - 138.0692
R² = 0.7410
0
0.5
1
1.5
2
2.5
3
3.5
RDXug/L
Date
EMW-08
Plume Wide Analysis
Plume Core Mass
Plume
Event
Number of
wells sampled
RDX mass
(g)
Change in mass from
Previous events
(g)
Percent
Change
1 16 3,693,903.46 N/A N/A
2 24 61,897,939.34 58,204,035.88 1576%
3 24 61,815,101.54 -82,837.80 0%
4 26 57,380,772.09 -4,434,329.45 -7%
 Insert example of plume core mass
wksheet
Statistical Mean
 The plume-wide statistical mean decreased
from 101 ppb at baseline in October 2007 to
42.38 ppb in December 2008
 Between December 2008 and December
2009, there was a 70.0% decrease in UCL
means to 12.73 ppb.
 However, based on the differential test
(Kolmogorov-Smirnov), the change in
populations is not statistically significant at a
95% confidence level.
 All data sets result from the same population

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Downey_MG_Maryland_Tt format

  • 1. Quantitative Metrics to Gage the Effects of an Enhanced Biodegradation Program Iowa Army Ammunitions Plant, Middletown, Iowa Melisa Geraghty, Brian Caldwell, PG; Dr. Tiffany Downey, Dr. Ronnie Britto, and Dr. Rick Arnseth
  • 2. Site History  Iowa Army Ammunition Plant (IAAAP) - located in Des Moines County, Iowa  Munitions production and testing beginning in 1941  Resulted in contamination of the soil, groundwater, and surface water with explosives – Extensive offsite Royal Demolition Explosive (RDX) groundwater plume sourced by RDX in surface water runoff.
  • 4. Remediation Plan  To enhance biodegradation and expedite the natural attenuation of the RDX plume using an enhanced degradation process (sodium acetate injection) – 11 designed-injection wells upgradient of the highest concentration plume core. – Analytically modeled injection rates and locations – Five injection events between October 2007 and April 2009 • initial event employed all 11 injection wells. • Subsequent events customized injected mass and number of injection points based on analytical data
  • 5. Development of Evaluation Metrics  Remedial progress metrics developed to account for temporal and spatial comparisons in order to maintain optimal reducing conditions – Quantitative analysis of plume configuration – Statistical analysis of the RDX concentrations from individual sampling events
  • 6. Evaluation Metrics Include  Point by point comparisons – Statistical trend analysis – First-order kinetics concentration change analysis • degradation rates and times to achieve remediation goals.  Plume wide analysis – Representative population using differential analysis – Central Tendency Analysis – Change in overall plume core mass.
  • 7. Mann-Kendall Trend Analysis  Non-parametric statistical test (the data are not required to be normally distributed)  Assesses point changes in a data set over time for an increasing or decreasing trend at a given statistical confidence level. – Designed to assess four to eighteen rounds of data at an 80% confidence level – Determines if the data can be used to estimate a first order degradation or augmentation rate – To avoid biasing the MK test, the same value for all ND results was used (one half of the detection limit from the round with the lowest detection limit for that well). – For wells that did not exhibit a increasing or decreasing trend at an 80% confidence level the coefficient of variation was used to determine if the well was stable or unstable
  • 8. Mann-Kendall Trend Analysis Con’t  For wells that did not have a minimum of four sampling events or did not exhibit an overall trend at 80% confidence, the last three measurements were used to approximate the direction of the concentration change.  The point-by-point analysis results indicate an overall decreasing trend in a majority of the wells. – 18 wells trended • 8 = decreasing • 1 = increasing • 9 = stable
  • 9. Quantifying a Decreasing Trend  Plotting of the log-transformed concentrations versus a linear unit of time (days were used). Finite source degradation is described by an exponential degradation curve when plotted on a linear scale. In order to use linear regression to calculate the slope (the degradation rate), the data were log- transformed and plotted on a linear scale.  Performing linear regression calculations on Step 1 by plotting a trend line (least-squares fit trend line) that minimizes the variance (squared deviations) of all of the data points from the line.  Using the slope of the equation represented by the least- squares trend line as the fractional change per day. This was then used to calculate a half-life expressed in days, and to develop a degradation curve that predicts the time at which the concentrations at that sampling point will reach 2 ppb.
  • 10. Example Output DATE RDX (ug/L) Ln Conc. (ug/L) Degradation Rate (% per day) 09/28/2007 104 4.644390899 1.021765998 12/19/2007 95.8 4.562262685 1.003697791 02/13/2008 76.9 4.342505877 0.955351293 12/09/2008 41.3 3.7208625 0.81858975 First-order Degradation Rate (day-1) = 0.0022 Half Life (days) = 315.05 Mann Kendall Statistic (S) = -6.0 Number of Rounds (n) = 4 Average = 79.50 Standard Deviation = 27.880 Coefficient of Variation(CV)= 0.351 Trend ≥ 80% Confidence Level DECREASING Trend ≥ 90% Confidence Level DECREASING
  • 11. Example Output Graphs - Decreasing y = -0.1440x + 5,771.5677 R² = 0.9731 0 20 40 60 80 100 120 RDXug/L Date EMW-06 y = -0.0022x + 90.2403 R² = 0.9880 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 LnRDXug/L Date EMW-06 0 5 10 15 20 25 30 35 40 45 0 200 400 600 800 1000 1200 1400 1600 Concentration(ug/L) Time (days) Degradation Curve
  • 12. Example Output Graphs – Stable or Non-Stable y = 0.0144x - 506.6684 R² = 0.0769 0 10 20 30 40 50 60 70 RDXug/L Date IW-05 y = 0.0523x - 1,978.1657 R² = 0.9245 0 10 20 30 40 50 60 RDXug/L Date IW-05
  • 13. Example Output Graphs - Increasing y = 0.0035x - 138.0692 R² = 0.7410 0 0.5 1 1.5 2 2.5 3 3.5 RDXug/L Date EMW-08
  • 15. Plume Core Mass Plume Event Number of wells sampled RDX mass (g) Change in mass from Previous events (g) Percent Change 1 16 3,693,903.46 N/A N/A 2 24 61,897,939.34 58,204,035.88 1576% 3 24 61,815,101.54 -82,837.80 0% 4 26 57,380,772.09 -4,434,329.45 -7%
  • 16.  Insert example of plume core mass wksheet
  • 17. Statistical Mean  The plume-wide statistical mean decreased from 101 ppb at baseline in October 2007 to 42.38 ppb in December 2008  Between December 2008 and December 2009, there was a 70.0% decrease in UCL means to 12.73 ppb.  However, based on the differential test (Kolmogorov-Smirnov), the change in populations is not statistically significant at a 95% confidence level.  All data sets result from the same population

Notes de l'éditeur

  1. Took the thickness of the potentiometric surface map converted to cubic feet then converted to liters multiplied by porosity . The result was multiplied by the actual RDX concentration.
  2. The 95% UCL Mean is the value that when calculated for the dataset distribution equals or exceeds the true mean 95% of the time.