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Passive sampling using integrative samplers enables the monitoring of munitions constituents in underwater environments over timescales of days to months and at ultra-low concentrations. Munitions compounds have an affinity for some resins and polymers that, when submerged for a period of time and corrected for the environment-specific sampling rate, can be used to determine time weighted average ambient water concentrations. This article primarily details the Polar Organic Chemical Integrative Sampler (POCIS), its optimization using laboratory flume and field experiments, and its application at munitions-impacted underwater sites.

Related Article(s):


CONTRIBUTOR(S): Dr. Guilherme Lotufo and Gunther Rosen

Key Resource(s):

Background

Figure 1. Underwater munitions are derived from UXO and historical disposal practices

Underwater unexploded ordnance (UXO) at active and former training ranges and discarded military munitions (DMM), collectively referred to as underwater munitions and explosives of concern (MEC), present challenges due to both immediate safety considerations (e.g. explosive blast) and potential ecological and human health impacts resulting from the release of munition constituents (MC) to the marine environment. Underwater sites around the world are known to contain MEC as a result of military activities or historic disposal events (Figure 1). MC including 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-triazine (RDX) may be released into the surrounding aquatic environments as a result of MEC corrosion and breaching of the munition’s outer casing[2][3][4][5][6][7][8][9]. Release may also occur from fragments of explosives formulations that become exposed following low-order (incomplete) detonations (LOD) resulting in fully breached munitions[9] (Figure 2).

Figure 2. Conceptual diagram of MC release from a breached underwater UXO.

The rate of release of MC from MEC into the surrounding environment is expected to be influenced by the size of the initial breach and growth of the breach hole in the munition casing, the radius of the cavity formed due to loss of MC mass from inside the MEC, the dissolution rate from solid to aqueous phases of the MC inside the MEC, the outside ambient current to which the casing breach hole is exposed, and the mass of MC remaining inside[4][10]. Subsequent to the breaching event, concentrations in the surrounding environment are expected to fluctuate over time because of the dependence of release kinetics on the above parameters, as well as hydrodynamic conditions leading to dilution effects, sorption to suspended particles, photo-transformation, and other factors leading to MC loss from the aquatic environment[6][11][12]. As a result of slow release and rapid removal of MC in the surrounding water[8][11][12], MC have been detected at low frequency relative to the number of samples examined and at low concentrations at Underwater Military Munitions (UWMM) sites[6][8][11]. Overall, munitions constituent persistence in the environment is a key determinant of exposure[11]. Exposure to MC in water has been shown to be toxic to aquatic organisms belonging to various taxonomic groups[8][11][13][14].

Underwater Sampling Challenges

Considering that MC are expected to be present at UWMM sites mainly at ultra-low concentrations and with concentrations decreasing with increasing distance from the source of released MC[7][15][16][1], a number of challenges prevent accurate assessment of environmental exposure using traditional water, sediment, and tissue sampling and analyses. These challenges include a high level of effort or difficulty required to:
     1. identify breached underwater MEC that are actually releasing MC;
     2. measure MC in the water column at low levels; and
     3. characterize water column exposure using the appropriate spatial and temporal scales for determining ecological risk.

Standard environmental sampling, such as grab sampling of surface water, only generates information for the time of sample collection, and spot grab sampling strategies may inadequately capture temporal changes[17] in MC concentrations that occur at UWMM sites, thereby providing an inaccurate measure of environmental exposure. In contrast, integrative passive sampling has been used to derive ultra-low and time-weighted water concentrations for a wide range of environmental contaminants[18], including MC[7][19][20][21][22][23]. Polar organic chemical integrative samplers (POCIS)[24] currently are the most widely used samplers for weakly hydrophobic contaminants (typically those with log Kow < 4).

The US Department of Defense’s Environmental Security Technology Certification Program (ESTCP) provided funding for research aimed at optimizing use of POCIS passive sampling technology for sampling MC in water and at demonstrating the application of POCIS to determine time-weighted average (TWA) water-column concentrations in the vicinity of MEC at a UWMM site (ESTCP Project ER‐201433)[1]. Some results of that project are presented in the following sections of this article.

Technology Overview

The POCIS consists of a receiving phase (sorbent) sandwiched between two polyethersulfone (PES) microporous membranes with ~0.1 μm pore size[24] (Figure 3). The sampler is held together by two stainless steel rings with an interior diameter of 51-54 mm, which provides an exposure surface area of 41-46 cm2. The POCIS are available commercially from Environmental Sampling Technologies (EST; St. Joseph, Missouri), and contain the widely used Oasis® hydrophilic-lipophilic balance (HLB) polymer as the sorbent. A variety of sampler holders and canisters have been used to protect the passive samplers in the field. The holder and canister shown in Figure 4 are commercially available from EST.

Figure 3. the structure of a POCIS where stainless steel encompasses the PES membranes and the adsorbent in the middle (from Morin et al. 2012 and Seethapathy et al. 2008)[25][26].


References

  1. ^ 1.0 1.1 1.2 Rosen, G., Colvin, M., George, R., Lotufu, G., Woodley, C., Smith, D. and Belden, J., 2017. Validation of passive sampling devices for monitoring of munitions constituents in underwater environments (No. SPAWAR-SCP-TR-3076). SPAWAR Systems Center Pacific San Diego. Report.pdf
  2. ^ Lewis, J., Martel, R., Trépanier, L., Ampleman, G. and Thiboutot, S., 2009. Quantifying the transport of energetic materials in unsaturated sediments from cracked unexploded ordnance. Journal of environmental quality, 38(6), pp.2229-2236. doi: 10.2134/jeq2009.0019 Free pdf download
  3. ^ Rosen, G. and Lotufo, G.R., 2010. Fate and effects of Composition B in multispecies marine exposures. Environmental toxicology and chemistry, 29(6), pp.1330-1337.Report.pdf
  4. ^ 4.0 4.1 Wang, P.F., Liao, Q., George, R. and Wild, W., 2011. Release rate and transport of munitions constituents from breached shells in marine environment. In Environmental chemistry of explosives and propellant compounds in soils and marine systems: Distributed source characterization and remedial technologies (pp. 317-340). American Chemical Society. doi: 10.1021/bk-2011-1069.ch016
  5. ^ Li, Y., Yang, C., Bao, Y., Ma, X., Lu, G. and Li, Y., 2016. Aquatic passive sampling of perfluorinated chemicals with polar organic chemical integrative sampler and environmental factors affecting sampling rate. Environmental Science and Pollution Research, 23(16), pp.16096-16103. doi: 10.1007/s11356-016-6791-1
  6. ^ 6.0 6.1 6.2 Voie, Øyvind A., and Espen Mariussen. "Risk assessment of sea dumped conventional munitions." Propellants, Explosives, Pyrotechnics 42, no. 1 (2017): 98-105. doi:10.1002/prep.20160
  7. ^ 7.0 7.1 7.2 Rosen, G., Lotufo, G.R., George, R.D., Wild, B., Rabalais, L.K., Morrison, S. and Belden, J.B., 2018. Field validation of POCIS for monitoring at underwater munitions sites. Environmental toxicology and chemistry, 37(8), pp.2257-2267. doi: 10.1002/etc.4159
  8. ^ 8.0 8.1 8.2 8.3 Beck, A.J., Gledhill, M., Schlosser, C., Stamer, B., Böttcher, C., Sternheim, J., Greinert, J. and Achterberg, E.P., 2018. Spread, behavior, and ecosystem consequences of conventional munitions compounds in coastal marine waters. Frontiers in Marine Science, 5, p.141. Report.pdf
  9. ^ 9.0 9.1 Beck, A.J., van der Lee, E.M., Eggert, A., Stamer, B., Gledhill, M., Schlosser, C. and Achterberg, E.P., 2019. In situ measurements of explosive compound dissolution fluxes from exposed munition material in the Baltic Sea. Environmental science & technology, 53(10), pp.5652-5660. doi: 10.1021/acs.est.8b06974
  10. ^ Wang, P. F., George, R. D., Wild, W. J., and Liao, Q., 2013. Defining munition constituent (MC) source terms in aquatic environments on DoD Ranges (ER-1453), Final Report. SSC Pacific Technical Report 1999. Strategic Environmental Research and Development Program (SERDP). Space and Naval Warfare Systems Center (SSC) Pacific: San Diego, CA Report.pdf
  11. ^ 11.0 11.1 11.2 11.3 11.4 Lotufo, G.R., Chappell, M.A., Price, C.L., Ballentine, M.L., Fuentes, A.A., Bridges, T.S., George, R.D., Glisch, E.J., Carton, G. 2017. Review and synthesis of evidence regarding environmental risks posed by munitions constituents (MC) in aquatic systems, Final report. SERDP Project ER-2341. ERDC/EL TR-17-17. US Army Corps of Engineers, Engineer Research and Development Center, Vicksburg, MS Report.pdf
  12. ^ 12.0 12.1 Tobias, C. 2019. Tracking the uptake, translocation, cycling, and metabolism of munitions compounds in coastal marine ecosystems using Stable Isotopic Tracer, Final Report. SERDP Project ER-2122. Report.pdf
  13. ^ Craig, H.D. and Taylor, S., 2011. Framework for evaluating the fate, transport, and risks from conventional munitions compounds in underwater environments. Marine Technology Society Journal, 45(6), pp.35-46. doi: 10.4031/MTSJ.45.6.10
  14. ^ Lotufo, G.R., Rosen, G., Wild, W. and Carton, G., 2013. Summary review of the aquatic toxicology of munitions constituents (No. ERDC/EL-TR-13-8). US Army Corps of Engineers, Engineer Research and Development Center, Vicksburg, MS Report.pdf
  15. ^ Rodacy, P.J., Reber, S.D., Walker, P.K. and Andre, J.V., 2001. Chemical sensing of explosive targets in the Bedford Basin, Halifax Nova Scotia. Sandia National Laboratories. Report.pdf
  16. ^ Porter, J.W., Barton, J.V. and Torres, C., 2011. Ecological, radiological, and toxicological effects of naval bombardment on the coral reefs of Isla de Vieques, Puerto Rico. In Warfare Ecology (pp. 65-122). Springer, Dordrecht. doi:10.1007/978-94-007-1214-0_8
  17. ^ Poulier, G., Lissalde, S., Charriau, A., Buzier, R., Cleries, K., Delmas, F., Mazzella, N. and Guibaud, G., 2015. Estimates of pesticide concentrations and fluxes in two rivers of an extensive French multi-agricultural watershed: application of the passive sampling strategy. Environmental Science and Pollution Research, 22(11), pp.8044-8057.
  18. ^ Roll, I.B. and Halden, R.U., 2016. Critical review of factors governing data quality of integrative samplers employed in environmental water monitoring. Water research, 94, pp.200-207. Open Access Manuscript
  19. ^ Belden, J.B., Lotufo, G.R., Biedenbach, J.M., Sieve, K.K. and Rosen, G., 2015. Application of POCIS for exposure assessment of munitions constituents during constant and fluctuating exposure. Environmental toxicology and chemistry, 34(5), pp.959-967. doi: 10.1002/etc.2836
  20. ^ Rosen, G., Wild, B., George, R.D., Belden, J.B. and Lotufo, G.R., 2016. Optimization and field demonstration of a passive sampling technology for monitoring conventional munition constituents in aquatic environments. Marine Technology Society Journal, 50(6), pp.23-32. doi: 10.4031/MTSJ.50.6.4
  21. ^ Lotufo, G.R., George, R.D., Belden, J.B., Woodley, C.M., Smith, D.L. and Rosen, G., 2018. Investigation of polar organic chemical integrative sampler (POCIS) flow rate dependence for munition constituents in underwater environments. Environmental monitoring and assessment, 190(3), p.171. doi: 10.1007/s10661-018-6558-x
  22. ^ Lotufo, G.R., George, R.D., Belden, J.B., Woodley, C., Smith, D.L. and Rosen, G., 2019. Release of Munitions Constituents in Aquatic Environments Under Realistic Scenarios and Validation of Polar Organic Chemical Integrative Samplers for Monitoring. Environmental toxicology and chemistry, 38(11), pp.2383-2391. doi: 10.1002/etc.4553
  23. ^ Estoppey, N., Mathieu, J., Diez, E.G., Sapin, E., Delémont, O., Esseiva, P., de Alencastro, L.F., Coudret, S. and Folly, P., 2019. Monitoring of explosive residues in lake-bottom water using Polar Organic Chemical Integrative Sampler (POCIS) and chemcatcher: determination of transfer kinetics through Polyethersulfone (PES) membrane is crucial. Environmental pollution, 252, pp.767-776. doi: 10.1016/j.envpol.2019.04.087
  24. ^ 24.0 24.1 Alvarez, D.A., Petty, J.D., Huckins, J.N., Jones‐Lepp, T.L., Getting, D.T., Goddard, J.P. and Manahan, S.E., 2004. Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments. Environmental Toxicology and Chemistry: An International Journal, 23(7), pp.1640-1648. doi:10.1897/03-603
  25. ^ Morin, N., Miège, C., Coquery, M. and Randon, J., 2012. Chemical calibration, performance, validation and applications of the polar organic chemical integrative sampler (POCIS) in aquatic environments. TrAC Trends in Analytical Chemistry, 36, pp.144-175. doi: 10.1016/j.trac.2012.01.007 Author's Manuscript
  26. ^ Seethapathy, S., Gorecki, T. and Li, X., 2008. Passive sampling in environmental analysis. Journal of Chromatography A, 1184(1-2), pp.234-253. doi: 10.1016/j.chroma.2007.07.070

See Also