Minwara 98
Minwara 98
Of all the buried landmine identification technologies currently                          II. CHEMICALS IN THE SOIL ENVIRONMENT
available, sensing the chemical signature from the explosive
components found in landmines is the only technique that can
                                                                                Soils are porous media with a number of physico-chemical
classify non-explosive objects from the real threat. In the last two            properties that affect the transport of explosive chemicals.
decades, advances in chemical detection methods have brought                    Soil bulk density is a measure of the compaction of the soil
chemical sensing technology to the foreground as an emerging                    and is defined as
technological solution. In addition, advances have been made in                                           M
the understanding of the fundamental transport processes that                                        ρb = s                              [1]
                                                                                                          Vs
allow the chemical signature to migrate from the buried source to
the ground surface. A systematic evaluation of the transport of the             where ∆b is the soil bulk density (g/cm3), Ms is the mass of
chemical signature from inside the mine into the soil environment,              soil particles (g), and Vs is the volume of soil (cm3). Soils
and through the soil to the ground surface is being explored to                 under natural conditions have bulk densities ranging from
determine the constraints on the use of chemical sensing                        1.0 to 1.8 g/cm3. However, soils that have been excavated
technology. This effort reports on the results of simulation                    and replaced, such as during the emplacement of a
modeling using a one-dimensional screening model to evaluate the                landmine, may have bulk densities much less than 1. The
impacts on the transport of the chemical signature by variation of              soil bulk density is inversely proportional to the soil
some of the principal soil transport parameters.
                                                                                porosity as follows
landmines, chemical sensors, soil transport                                                          φ = 1 − ρb / ρs                     [2]
                                                                                where ∆s is the soil particle density (ranges from 2.6 to 2.8
                        I. INTRODUCTION                                         g/cm3 for most soils). The soil porosity, or void volume, is
                                                                                defined as
The organic chemicals of the explosives in the buried                                                      Vw + Va
landmine environment can exist in or on four phases: solid                                           φ=                                       [3]
                                                                                                             Vs
phase of the neat explosive material, vapor phase in the soil
air, aqueous phase in the soil water solution, and sorbed                       where Ν is the soil porosity (cm3/cm3), Vw is the volume of
onto soil solid phases. The chemical signature begins as a                      soil water (cm3) and Va is the volume of soil air (cm3). Soil
surface coating from production or depot storage and                            porosity values range from 0.3 for sands to 0.6 for clay rich
through continuous emission by permeation through the                           soils. The volumetric moisture content describes how much
mine case or through leaks in seals and seams. Once the                         water is present in the soil and changes greatly during
chemicals enter the soil environment, they experience phase                     precipitation/drainage events and evaporation conditions.
transitions, partitioning into the soil air, soil water and                     Volumetric water content is defined as
sorbing onto soil particles. The impact of temperature and                                                 Vw
chemical gradients, and precipitation/evaporation will cause
                                                                                                     θ=                                       [4]
                                                                                                           Vs
movement of the chemical signature. Part of this transport
                                                                                where 2 is the volumetric water content (cm3/cm3). Soil
is upward to the soil surface where chemical detection
                                                                                moisture contents have values from near zero up to the soil
technology is envisioned to be used. Simulation modeling
                                                                                porosity value. When the soils are not fully saturated, the
is a technique that can evaluate the impacts of many of the
                                                                                balance of the soil pore space not filled with water is termed
environmental variables that can dampen or accentuate the
                                                                                the air filled porosity, and is defined as
surface expression of the chemical signature. Model results
will be shown that describe the magnitude of the changes                                                      Va
                                                                                                        a=                                    [5]
that accompany variations due to chemical properties of the                                                   Vs
explosive and properties of the soil environment.
                                                                                where Va is the volumetric air content (cm3/cm3).
The above model results in a closed form solution as a                       Table 2. Simulation Parameters
function of space and time; the results are rather lengthy and     parameter       units        base case variant
will not be presented here but are given by Jury et al. (1983,                                              cases
1990). In the present simulation, the assumption of constant     θ             cm3/ cm3        0.25         0.375
water flux in time will be relaxed. Therefore, sequences of
water fluxes representing desired conditions (rainfall           φ                cm3/ cm3        0.5           *
followed by evaporation) can be simulated to determine the       ρb               g/cm3           1.5           *
effect of water flux variations on the location of TNT in the    Kd               cm3/g           1.6           3.8
soil and the surface TNT vapor flux. A numerical solution                                                       6.0
was developed and verified by comparison to the results          KH               --              5.9E-7        4.73E-10
given by Spencer et al. (1988) and Jury et al. (1990)            air boundary     cm              0.5           *
(Phelan and Webb, 1997).                                         layer
                                                                 t1/2             days            365           180
Using this solution, simulations were performed using a                                                         60
landmine that has contributed an initial soil concentration      Co               µg/cm3          4.6E-3        0
(Co) based on the surface contamination of the landmine. It      Jc               µg/cm2-day      8.6E-6        0
has been assumed that the entire surface contamination was       Dlw              cm2/day         0.432         *
completely and uniformly transferred to the soil just prior to
                                                                 Dga              cm2/day         4320          *
the beginning of the simulation runs. Surface contamination
data (Hogan et al., 1992) showed a median surface                burial depth,    cm              10            *
contamination of 15 ng/cm2 from 42 domestic and foreign          top
landmines. Using the dimensions of an anti-tank (AT) mine        burial depth,    cm              20            *
of 30 cm diameter by 10 cm high, the surface contamination       bottom
would provide 3.5x10-5 g of TNT for initial distribution in      cycles/yr        --              45            *
the soil. Using the volume of the AT mine that this mass of      precipitation    days            1             *
TNT is distributed into, the initial concentration (Co) would    evaporation      days            7             *
be ~5x10-3 µg/cm3.                                               precipitation    cm/day          0.44          *
                                                                 rate
The constant source term emanation rate was derived from         evaporation      cm/day          - 0.063       *
vapor collection chamber experiments on two mines                rate
(Spangler, 1975). Values ranged from 10-16 to 10-18 g/cm2-       total            cm/year         20            *
s. The higher rate of 10-16 g/cm2-s (8.6x10-6 µg/cm2-day)        precipitation/
was used in these simulations. If the top of the AT mine         evaporation
was buried at a depth of 10 cm, the burial zone of the initial   * - same as the base case
contamination is from 10 to 20 cm, and the constant source
term is placed at a depth of 15 cm.                                                      V. DISCUSSION
                                 a                               For each of the figures shown, there is a distinct oscillation
The diffusivity of gas in air ( Dg ) and diffusivity of liquid   of the surface vapor flux. This feature is a result of the
             w
in water ( Dl ) were selected from Jury et al. (1983). The       cycling of precipitation and evaporation. To evaluate the
                                                                 effect of the Henry’s Law constant, two simulations were
biochemical half-life value of 365 days was selected from a      performed where all parameters were kept constant with one
long term field experiment (Dubois and Bayton, 1991).            case using a KH equal to that of TNT and one for RDX
                                                                 (both at 20°C). Figure 1 shows the results and indicate that
The precipitation/evaporation rates and periods followed in
                                                                 the TNT surface vapor flux would be expected to reach a
all the simulations here were the low desert scenario from
                                                                 greater steady state value than RDX, approximately
Phelan and Webb (1997). This scenario was derived from
                                                                 proportional to the ratio of Henry’s Law constants. For
data found in HELP (Hydrological Evaluation of Landfill
                                                                 TNT, a temperature increase from 0°C to 40°C will increase
Performance) model (Schroeder et al., 1994a and 1994b). .
                                                                 the KH value by a factor of about 100. It appears that
The HELP model showed that the low desert had 1 day of           seasonal and diurnal soil temperature changes could make a
precipitation followed by 7 days of evaporation. For             significant effect on the subsurface transport and surface
simplicity, total precipitation and total evaporation for each   flux of explosive signatures.
cycle are assumed to be equal and for these simulations the
cycles were continued for approximately four to ten years.
                                                             1.00E+00
                                                             1.00E-01
                                                             1.00E-02
                                                             1.00E-03
                                                             1.00E-04
                                                             1.00E-05
                                                             1.00E-06
                                                             1.00E-07
Depth concentration profiles at the end of the simulation                                                            Next, simulations were performed to evaluate small changes
period show that for both cases the concentration of TNT                                                             in the soil water partitioning coefficient. The Kd values for
and RDX are essentially equal. This implies that most of                                                             TNT, DNT and RDX have values from about 1.5 to 7.
the transport upward to the ground surface is within the                                                             Figure 2 shows the surface flux over time for Kd values of
aqueous phase and that the release of the chemical into the                                                          1.6, 3.8 and 6.0 cm3/g.
vapor phase above the ground surface is directly
proportional to the Henry’s Law constant.
                                                             1.00E+00
                                                             1.00E-01
                                                             1.00E-02
                                                             1.00E-03
                                                             1.00E-04
                                                             1.00E-05
                                                             1.00E-06
                                                             1.00E-07                                                                        Kd
                           Surface Vapor Flux (ug/cm2-day)
                                                             1.00E-08
                                                                                                                                             1.6
                                                             1.00E-09
                                                             1.00E-10
                                                             1.00E-11                                                                        3.8
                                                             1.00E-12
                                                                                                                                             6.0
                                                             1.00E-13
                                                             1.00E-14
                                                             1.00E-15
                                                             1.00E-16
                                                             1.00E-17
                                                             1.00E-18
                                                             1.00E-19
                                                             1.00E-20
                                                                                 1      2         3
                                                             1.00E-21
                                                             1.00E-22
                                                             1.00E-23
                                                                        0       200     400      600      800         1000    1200    1400         1600
                                                                                                       Time (days)
These simulations show that even though the soil water                                                               evaporation cycles becomes more pronounced. This is
partitioning coefficients appear to vary only slightly among                                                         consistent with the lower Kd value, since more of the mass
many soils, there is a significant impact to the transport of                                                        of the chemical is found in the aqueous phase and is
the chemical to the ground surface. As the Kd value                                                                  affected by the upward and downward flux of water. Figure
increases, the lag period becomes much longer and the                                                                3 shows the depth profiles from the simulations varying the
steady state concentrations stabilize at much lower levels.                                                          soil water partitioning coefficients. These curves show that
Also with the lower Kd values, the effect of precipitation/                                                          the simulations with lower Kd values have more significant
transport of the chemicals to soils both above and below the                                                            source zone than the higher Kd values.
                                                          2.50E-03
Kd = 6
2.00E-03
Kd = 3.8
Kd = 1.6
1.00E-03
5.00E-04
                                                          0.00E+00
                                                                     0             5         10             15                   20               25              30
                                                                                                        Depth (cm)
The next simulations were an evaluation of the source term                                                              and the amount from the surface emission flux (0.02
parameters. Very little data is available on the initial                                                                ug/day), it would take about 4.8 years for the total mass of
concentration of explosives coating the outer surface of a                                                              explosive from the surface emission flux to equal the
mine and even less so on the surface emission flux. Figure                                                              amount from the initial surface contamination. Curve two
4, curve one shows the effect of reducing the surface                                                                   in Figure 4 shows the effect where the initial concentration
emission flux to essentially zero (a value of 1E-20 ug/cm2-                                                             on the mine is essentially zero (a value of 1E-20 ug/cm3
day was used). This curve is essentially the same as curve                                                              was used). This shows a significantly longer lag time and
one in Figure 1 where the surface emission flux (Jc) was                                                                about four orders of magnitude lower steady state surface
equal to 8.6E-6 ug/cm2-day. This implies that the surface                                                               vapor flux at the end of the simulation period. Figure 4
emission flux makes very little contribution to the overall                                                             indicates that the initial concentration is a much more
mass transport in the soil. If one considers the total mass of                                                          important parameter than the surface flux for the mass
explosive contributed by the initial concentration (35 ug)                                                              transport of chemicals to the ground surface.
                                                          1.00E+00
                                                          1.00E-01
                                                          1.00E-02
                                                          1.00E-03
                                                          1.00E-04
                                                          1.00E-05
                                                          1.00E-06
                                                          1.00E-07
                        Surface Vapor Flux (ug/cm2-day)
                                                                                                                 Co = 4.6E-3 ug/cm3
                                                          1.00E-08
                                                                                                                 Jc = 1E-20 ug/cm2-day (approximates zero)
                                                          1.00E-09
                                                          1.00E-10
                                                                                                                                                           1
                                                          1.00E-11
                                                          1.00E-12
                                                          1.00E-13
                                                          1.00E-14
                                                          1.00E-15
                                                                                                                                                           2
                                                          1.00E-16
                                                          1.00E-17
                                                          1.00E-18
                                                                                                                        Co = 1E-20 ug/cm3 (approximates zero)
                                                          1.00E-19
                                                                                                                        Jc = 8.6E-6 ug/cm2-day
                                                          1.00E-20
                                                          1.00E-21
                                                          1.00E-22
                                                          1.00E-23
                                                                     0       200       400        600      800            1000         1200         1400        1600
                                                                                                        Time (days)
1.00E+00
1.00E-01
1.00E-02
1.00E-03
                                                           1.00E-04
                                                                                                                            Co = 4.6E+2 ug/cm3
                                                           1.00E-05
                                                                                                                                                                     1
                         Surface Vapor Flux (ug/cm2-day)
                                                           1.00E-06
1.00E-07
                                                           1.00E-08
                                                                                                                             Co = 4.6E-2 ug/cm3
                                                           1.00E-09
                                                                                                                                                                     2
                                                           1.00E-10
                                                                                                                                                                     3
                                                           1.00E-11
                                                           1.00E-12
                                                                                                                                     Co = 4.6E-3 ug/cm3
                                                           1.00E-13
1.00E-14
1.00E-15
1.00E-16
1.00E-17
1.00E-18
                                                           1.00E-19
                                                                      0       200         400               600             800           1000      1200     1400        1600
                                                                                                                       Time (days)
Another parameter where there is very little data is the                                                                                 (curve 2). Figure 6 shows that over the long-term, the
biochemical half life (t1/2). There are many influences on                                                                               shorter half-life will significantly decrease the steady state
the magnitude of this parameter and the variability is                                                                                   surface flux. Biochemical decay constants that are very
expected to be large. Simulations over ten (10) years were                                                                               large (e.g. RDX values over 30 years) appears to have
completed to assess the impact of decreases in the                                                                                       minimal impact to the short term soil transport phenomena
biochemical half-life from 365 days (curve 1) to 180 days                                                                                evaluated in these simulations.
                                                           1.00E+00
                                                           1.00E-01
                                                           1.00E-02
                                                           1.00E-03
                                                           1.00E-04
                                                           1.00E-05
                                                           1.00E-06
                                                           1.00E-07
                         Surface Vapor Flux (ug/cm2-day)
                                                           1.00E-19
                                                                                                                                         3
                                                           1.00E-20
                                                           1.00E-21
                                                           1.00E-22
                                                           1.00E-23
                                                                      0      500      1000           1500            2000         2500       3000     3500    4000       4500
                                                                                                                       Time (days)
Initial simulations using this approach showed that for a                                                                                greater steady state concentrations. Figure 7 shows how
particular scenario, the constant moisture content value had                                                                             increasing the soil saturation from 0.5 to 0.75, decreases the
a significant impact on the lag period (when the vapor flux                                                                              lag period substantially and increases the steady state
reached the ground surface) and the steady state                                                                                         surface flux by two orders of magnitude. The constant
concentrations (Phelan and Webb, 1997). Higher moisture                                                                                  moisture content assumption in this screening model allows
contents showed significantly shorter lag periods and                                                                                    for a simplified mathematical solution to complex transport
phenomena. One must recognize this assumption and not                                                           transport phenomena of chemical signatures from buried
over generalize the information gleaned from these                                                              landmines in more detail and with fewer simplifying
simulations. Future efforts will include the development of                                                     assumptions.
a numerical simulation capability that can explore the
                                                      1.00E+00
                                                      1.00E-01
                                                      1.00E-02
                                                      1.00E-03
                                                      1.00E-04
                                                      1.00E-05
                                                      1.00E-06
                                                      1.00E-07                                                    Sl=0.75
                                                                                                                                                        1
                         Surface Flux (ug/cm2-day)
                                                      1.00E-08
                                                      1.00E-09
                                                      1.00E-10
                                                                                                                                                        2
                                                      1.00E-11
                                                      1.00E-12
                                                                                                                   Sl=0.5
                                                      1.00E-13
                                                      1.00E-14
                                                      1.00E-15
                                                      1.00E-16
                                                      1.00E-17
                                                      1.00E-18
                                                      1.00E-19
                                                      1.00E-20
                                                      1.00E-21
                                                      1.00E-22
                                                      1.00E-23
                                                                 0    200     400      600          800            1000          1200           1400         1600
                                                                                                Time (days)
In some parts of the world, minefields are located in areas                                                     followed by -0.5 cm/day of evaporation for 60 days. This
that experience very distinct wet and dry climatic periods.                                                     shows the immediate drop in the steady-state surface flux
Figure 8 shows the result of a simulation to assess the effect                                                  after precipitation begins. Once the evaporation period
of a short-term continuos precipitation period followed by a                                                    begins, there is a short lag period where the surface vapor
short-term evaporation period. The baseline simulation                                                          flux stays nearly constant before rising to just above the flux
(Figure 1, curve 1) was run for 1440 days followed by 1                                                         before the precipitation began.
cm/day of precipitation for 30 days which was then
1.00E+00
1.00E-02
1.00E-04
                                                                                                              Precipitation begins
                                                      1.00E-06
                                                      1.00E-08
                          Surface Flux (ug/cm2-day)
1.00E-10
1.00E-12
1.00E-14
1.00E-16
1.00E-18
1.00E-20
                                                                                                                                        Evaporation begins
                                                      1.00E-22
                                                      1.00E-24
                                                             1200      1250     1300         1350         1400               1450             1500           1550
                                                                                                Time (days)